JPH04334384A - Spiroorthocarbonate compound - Google Patents

Abstract

PURPOSE:To obtain a new spiroorthocarbonate compound useful as a raw material for various kinds of molding materials, composite material, sealing material, coating compound, etc., because of exhibition of volume expansion by radical ring opening isomerization polymerization. CONSTITUTION:A compound shown by formula I (R<1> to R<12> are H or lower alkyl; R<13> are R<16> are H, lower alkyl, halogen, amino, etc.) such as a compound shown by formula II. The compound shown by formula I, for example, is obtained by reacting a dihaloaryloxymethane shown by formula III (Ar is aromatic group; X is halogen) is dehydrohalogenated with a diol compound shown by formula IV in the presence of trimethylamine in an atmosphere of an inert gas at -20 to 50 deg.C to give a dioxepane compound shown by formula V and the compound shown by formula V and a diol compound shown by formula VI are subjected to dearylol treatment in the presence of an acid catalyst such as p-toluenesulfonic acid in an atmosphere of an inert gas at -20 to 50 deg.C.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to novel spiro-orthocarbonate compounds. The compound of the present invention is a novel polymerizable compound and is useful as a raw material for molding materials, composite materials, casting materials, sealing materials, medical materials, dental materials, paints, adhesives, and the like.

0002

BACKGROUND OF THE INVENTION It is well known that polymerizable monomers such as acrylonitrile, vinyl acetate, methyl methacrylate, styrene, ethylene oxide, and epichlorohydrin undergo large shrinkage when polymerized. Further, volumetric shrinkage when thermosetting resins such as epoxy resins and phenolic resins harden has become a major problem in the fields of casting materials, sealing materials, adhesive materials, and the like.

[0003] If a material that exhibits non-shrinkage properties during polymerization can be created, improvements in dimensional accuracy, precision molding by reducing warpage, distortion, and gap formation, and improvements in material strength and adhesive strength by reducing internal stress can be expected. can.

[0004] Conventionally, it has been reported that some types of spiro-orthocarbonate compounds exhibit a very small decrease in volume or an increase in volume due to ring-opening isomerization polymerization, and their use in the various uses mentioned above has been reported. Applications are attracting attention.

The ring-opening isomerization polymerization method for spiro-orthocarbonate compounds includes a cationic polymerization method using a Lewis acid such as a boron trifluoride/ether complex and/or a Brønsted acid such as trifluoromethanesulfonic acid as a polymerization initiator. Methods using polymerization and radical polymerization using an azobis-based compound such as azobisisobutyronitrile and/or an organic peroxide such as benzoyl peroxide are known.

[0006]

[Problems to be Solved by the Invention] The ring-opening isomerization polymerization method of spiro-orthocarbonate compounds by cationic polymerization using Lewis acids and/or Brønsted acids as polymerization initiators is difficult because Lewis acids and Brønsted acids are usually strong acids. Because of this, it is difficult to handle, the influence of moisture on polymerization is large, and there are problems such as coloring of the obtained polymer and corrosivity and toxicity of the acid component remaining in the polymer.

On the other hand, the ring-opening isomerization polymerization method of spiro-orthocarbonate compounds by radical polymerization using an azobis compound and/or an organic peroxide as a polymerization initiator is as follows.
Although the problems seen in cationic polymerization methods using Lewis acids and/or Brønsted acids are not usually observed, only a small number of monomers undergo ring-opening isomerization and exhibit polymerization expansion through radical polymerization, and There was a problem in that the ring-opening isomerization rate was low, and as a result, the polymerization expansion rate was low.

An object of the present invention is to provide a spiro-orthocarbonate compound which undergoes ring-opening isomerization polymerization by radical polymerization and has a high polymerization expansion rate.

[0009]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on spiro-orthocarbonate compounds which undergo ring-opening isomerization polymerization by radical polymerization and have a large polymerization expansion coefficient. As a result, the present inventors discovered that a spiro-orthocarbonate compound having a specific structure undergoes ring-opening isomerization polymerization through radical polymerization and has a large polymerization expansion rate, leading to the completion of the present invention.

That is, the present invention is based on the following chemical formula 1.

[0011]

[Formula 1] (wherein, R1, R2, R3, R4, R5, R6
, R7, R8, R9, R10, R11 and R12 each represent a hydrogen atom or a lower alkyl group, R13, R1
4, R15 and R16 each represent a hydrogen atom, a lower alkyl group, an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group or an ester group. ) is related to a spiro-orthocarbonate compound represented by

In the above chemical formula 1, R1, R2, R3, R4,
The lower alkyl groups represented by R5, R6, R7, R8, R9, R10, R11 and R12, respectively, include alkyl groups having 8 or less carbon atoms, such as methyl group, ethyl group, n-
Examples include propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc., and R1
3, R14, R15 and R16 each represent a lower alkyl group having 8 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples include n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and examples of alkyloxy groups include methyloxy group and ethyloxy group. , n-propyloxy group, i-propyloxy group, n-butyloxy group, n-pentyloxy group, etc.; halogen groups include, for example, chloro group, bromo group, etc., and amino groups include, for example, N Examples of the amide group include an aminocarbonyl group and a formylamino group; examples of the ester group include a methoxycarbonyl group and an acetyloxy group. It will be done.

Preferred examples of the spiro-orthocarbonate compounds of the present invention include the following compounds.

[0014]

[Case 2]

The spiro-orthocarbonate compound of the present invention may be used not only as a single compound but also as a mixture of two or more compounds.

The spiro-orthocarbonate compound of the present invention may be used as a mixture with other polymerizable monomers. Other polymerizable monomers may be those having radical polymerizability, and preferred examples include acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, and styrene.

The method for producing the spiro-orthocarbonate compound shown in Formula 1 is not particularly limited. Examples of industrially advantageous manufacturing methods are as follows.

That is, the following chemical formula 3

[0019]

[Chemical formula 3]

A dihalodiaryloxymethane compound represented by the formula (wherein, Ar is an aromatic group and X is a halogen group) and the following compound

[0021]

[C4]

(In the formula, R1, R2, R3, R4, R5,
R6, R7 and R8 each represent a hydrogen atom or a lower alkyl group. ) by dehydrohalogenating the diol compound represented by the formula 5 below.

[0023]

[C5]

(In the formula, Ar is an aromatic group, R1, R2, R
3, R4, R5, R6, R7 and R8 each represent a hydrogen atom or a lower alkyl group. ) is produced, and the dioxepane compound represented by Chemical Formula 5 and the following Chemical Formula 6 are prepared.

[0025]

[C6]

(wherein R9, R10, R11 and R1
2 each represents a hydrogen atom or a lower alkyl group, R
13, R14, R15 and R16 each represent a hydrogen atom, a lower alkyl group, an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group or an ester group. ) A method for producing a spiro-orthocarbonate compound represented by Chemical Formula 1 by dealyrolling a diol compound represented by Chemical Formula 3, or a dihalodiallyloxymethane compound represented by Chemical Formula 3 and a diol compound represented by Chemical Formula 6. By dehydrohalogenating, the following chemical formula 7 can be obtained.

[0027]

[C7]

(In the formula, Ar is an aromatic group, R9, R10,
R11 and R12 each represent a hydrogen atom or a lower alkyl group, and R13, R14, R15 and R16 each represent a hydrogen atom, a lower alkyl group, an alkyloxy group, a halogen group, a nitro group, a cyano group, an amino group, an amide group, a hydroxyl group Or represents an ester group. ) A preferred method is to produce a spiro-orthocarbonate compound represented by Chemical Formula 1 by producing a dioxepane compound represented by Chemical Formula 7 and dealyrolling the dioxepane compound represented by Chemical Formula 7 and a diol compound represented by Chemical Formula 4.

In the dihalodiaryloxymethane compound represented by the above formula 3, examples of the aromatic group represented by Ar include phenyl group, p-methylphenyl group, p-ethylphenyl group, p-propylphenyl group, p-propylphenyl group, -phenylphenyl group, 1-naphthyl group, 2-naphthyl group, etc.,
Examples of the halogen group represented by include a chloro group, a bromo group, and an iodo group.

The dehydrohalogenation reaction between the dihalodiallyloxymethane compound represented by Chemical Formula 3 and the diol compound represented by Chemical Formula 4 or Chemical Formula 6 can be performed by This is carried out by mixing a diol compound represented by Chemical Formula 6 in the presence of an amine such as trimethylamine, triethylamine, or tri-n-propylamine. The dihalodiallyloxymethane compound represented by Chemical Formula 3 and the diol compound represented by Chemical Formula 4 or Chemical Formula 6 are preferably mixed in equimolar amounts. The amine is used in an amount of 200 to 400 mol%, preferably 200 to 300 mol%, based on the compound represented by Chemical Formula 3.

[0031] The reaction temperature is in the range of -78 to 100°C, preferably -20 to 50°C. The reaction is usually carried out in an inert gas atmosphere such as nitrogen, argon, helium, etc.

Although the above reaction may be carried out in the absence of a solvent, it is preferable to carry out the reaction in the presence of a solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform, or tetrachloroethylene to remove the reaction heat and facilitate the operation. This is preferable in terms of ease of use, etc.

[0033] The reaction time is usually selected within the range of 1 to 100 hours. After reaching the desired conversion rate, the reaction solution is washed with water, and then compound 5 or compound 7 obtained by a known method
A dioxepane compound represented by is isolated and purified.

Dioxepane compound shown by chemical formula 5 and chemical formula 6
A dealylol reaction with a diol compound shown by Chemical Formula 5 or a deallyol reaction between a dioxepane compound shown by Chemical Formula 7 and a diol compound shown by Chemical Formula 4 is carried out between a dioxepane compound shown by Chemical Formula 5 and a diol compound shown by Chemical Formula 6, or This is carried out by mixing the dioxepane compound represented by Chemical Formula 7 and the diol compound represented by Chemical Formula 4 in the presence of an acid catalyst such as p-toluenesulfonic acid or benzenesulfonic acid. A dioxepane compound represented by chemical formula 5, and a dioxepane compound represented by chemical formula 6
It is preferable that the diol compound represented by Formula 7 or the dioxepane compound represented by Chemical Formula 7 and the diol compound represented by Chemical Formula 4 be mixed in equimolar amounts. The acid catalyst is used in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the dioxepane compound represented by Chemical Formula 5 or Chemical Formula 7.

The reaction temperature is -78 to 100°C, preferably -20 to 50°C. The reaction is usually carried out in an inert gas atmosphere such as nitrogen, argon, helium, etc.

Although the above reaction may be carried out in the absence of a solvent, it is preferable to carry out the reaction in the presence of a solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform, or tetrachloroethylene to remove the reaction heat and improve the operation. This is preferable in terms of ease of use, etc.

[0037] The reaction time is usually selected within the range of 1 to 100 hours. After reaching the desired conversion rate, the reaction solution is washed with an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, and the spiro-orthocarbonate compound represented by formula 1 obtained by a known method is isolated and purified. .

The spiro-orthocarbonate compound of the present invention is subjected to ring-opening isomerization polymerization using a cationic polymerization catalyst such as boron trifluoride/ether complex, and is produced by azobisisobutyronitrile, methyl azobisisobutyrate, azobis-2,4 −
Azobis-based polymerization initiators such as dimethylvaleronitrile and azobiscyclohexanecarbonitrile; diisopropyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, dicumyl peroxide , G-t
Ring-opening isomerization polymerization is carried out using a radical polymerization initiator such as a peroxide polymerization initiator such as -butyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

[0039] Also, benzophenone, Michler's ketone,
Aromatic ketones such as xanthone, thioxanthone, 2-chlorothioxanthone, 2-ethylanthraquinone; acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2
-Methyl-4'-isopropylpropiophenone, 1-
Ultraviolet radical polymerization using initiators such as acetophenones such as hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-acetophenone benzyl dimethyl ketal, etc. , norcamphorquinone/N,N-dimethylaminoethyl methacrylate, camphorquinone/N,N-dimethylaminoethyl methacrylate, camphorquinone/p-N,N-dimethylaminoethyl benzoate, and other alpha-diketone/amine initiators. Visible light radical polymerization using .

The above-mentioned radical polymerization initiator has a ratio of 0.0 to the spiro-orthocarbonate compound represented by Formula 1.
It is used in a range of 1 to 10 mol%, preferably 0.05 to 3 mol%.

The temperature of the radical polymerization reaction varies depending on the type of radical polymerization initiator used, but ranges from room temperature to 20°C.
A temperature in the range 0°C, preferably 50-180°C is selected.

The radical polymerization reaction can be carried out under any pressure from reduced pressure to increased pressure, but is preferably carried out at normal pressure.

The radical polymerization reaction may be carried out in the absence of a solvent; however, aromatic hydrocarbons such as benzene, toluene, xylene, hemimelitene, pseudocumene, and mesitylene; aliphatic hydrocarbons such as hexane, heptane, and octane; The reaction may be carried out in the presence of a solvent such as an alicyclic hydrocarbon such as cyclohexane or cyclooctane; or a halogenated hydrocarbon such as methylene chloride, chloroform, tetrachloroethylene, chlorobenzene, dichlorobenzene, or trichlorobenzene.

The radical polymerization reaction time is usually selected within the range of 1 to 100 hours. After reaching the desired degree of polymerization,
The obtained polymer is isolated and purified by a known method.

[0045]

[Examples] The present invention will be explained in more detail with reference to Examples below. In addition, the physical property values were measured by the following method. 1H-NMR: JEOL PMX60SI type (measurement frequency: 60MHz) IR: JASCO Corporation Fourier transform infrared spectrophotometer FT
/IR-3 type melting point: Yanagimoto Seisakusho micro melting point measuring device MP type elemental analysis:
Yanagimoto Seisakusho CHN-Coder MT2 type Number average molecular weight and molecular weight distribution: Tosoh GPC-8000 system (
Polystyrene gel column; TSK gel G5000HXL
, G4000HXL, G2500HXL, mobile phase solvent;
THF, flow rate: 1.0 mL/min, detector: RI, polystyrene equivalent value) Density: Density gradient tube method specific gravity measuring device type A manufactured by Shibayama Kagaku Kikai Seisakusho (density gradient liquid; calcium bromide aqueous solution, measurement temperature;
25℃)

Example 1 The inside of a 200 mL glass flask equipped with a stirring device was sufficiently purged with dry nitrogen gas. 2 in the container
-methylene-1,4-butanediol 10.2 g (10
0 mmol), triethylamine 20.2 g (200 m
mol) and 50 mL of dry methylene chloride, and to this solution was added 26.91 g of dichlorodiphenoxymethane (
A solution of 100 mmol) of dry methylene chloride in 25 mL was added over 40 minutes while cooling with ice water. 1 at room temperature
After stirring for 3 hours, the reaction solution was washed twice with 100 mL of water,
The organic layer was dried over anhydrous sodium sulfate, concentrated, and distilled under reduced pressure to obtain 20.40 g of a colorless and transparent liquid with a boiling point of 158-161° C./0.3 mmHg. This liquid has 1H-NMR
It was identified as 2,2-diphenoxy-5-methylene-1,3-dioxepane from the spectrum and IR spectrum. The isolated yield was 68%.

1H-NMR spectrum (the results are shown in Figure 1)
) Measurement solvent; deuterated chloroform internal standard; tetramethylsilane

[0048]

[Chemical formula 8]

[0049]

[Table 1]

IR spectrum (results are attached as Figure 2)

The inside of a 200 mL glass container equipped with a stirring device was sufficiently purged with dry nitrogen gas. The 2,2-diphenoxy-5 obtained in the above reaction is placed in the container.
-methylene-1,3-dioxepane 10.44 g (35
mmol), p-toluenesulfonic acid monohydrate 270m
g (1.41 mmol) and dry methylene chloride 4
0 mL was charged, and 4.84 g (35 mmol) of orthoxylylene glycol was added to the solution at room temperature. After stirring at room temperature for 18 hours, the reaction solution was washed three times with 40 mL of 1N aqueous sodium hydroxide solution, and the organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous sodium sulfate and then concentrated to precipitate a white solid. The white solid was dissolved in n-hexane/
Purified by recrystallization with a mixed solution of ethyl acetate = 1/1,
7.39 g of colorless crystals were obtained. This solid is 1H-NMR
From the spectra and IR spectra, spiro[1,5-
It was identified as dihydro-5'-methylene-2,4-benzodioxepine-3,2'-[1,3]dioxepane]. The isolated yield was 85%.

Elemental analysis

[0053]

[Table 2]

Melting point: 114-116°C

1H-NMR spectrum (the results are shown in Figure 3)
) Measurement solvent; deuterated chloroform internal standard; tetramethylsilane

[0056]

[Chemical formula 9]

[0057]

[Table 3]

IR spectrum (results are attached as Figure 4)

[0059] Density: 1.318

Example 2 In Example 1, 10.2 g (100 mmol) of 2-methylene-1,4-butanediol was replaced with 1,3,4
The reaction was carried out in the same manner except that 14.4 g (100 mmol) of -trimethyl-2-methylene-1,4-butanediol was used. -methylene-4',6',7'
-trimethyl-3,2'-[1,3]dioxepane]6
．． 31 g was obtained.

Elemental analysis

[0062]

[Table 4]

Example 3 In Example 1, ortho-xylylene glycol 4.8
The reaction was carried out in the same manner except that 6.04 g (35 mmol) of 4-chloroorthoxylylene glycol was used instead of 4 g (35 mmol), and spiro[7-chloro-1,
5-dihydro-5'-methylene-2,4-benzodioxepine-3,2'-[1,3]dioxepane] 7.90
I got g.

Elemental analysis

[0065]

[Table 5]

Reference Example 1 Spiro[1,5-dihydro-5'-methylene-2,4-benzodioxepine-3,2'-[1,
3] Dioxepane] 248 mg and t-butyl hydroperoxide 2.7 mg were placed in a glass container, degassed, sealed, and heated at 180° C. for 4 hours to obtain a pale yellow transparent solid. Dissolve this solid in 2 mL of methylene chloride and
It was reprecipitated in 50 mL of hexane to obtain 50 mg of a transparent liquid. The number average molecular weight of the product is 1380, and the molecular weight distribution is 1.
It was 97.

When the IR spectrum of the product was measured, absorption due to carbonate of the ring-opened polymer was observed at 1753 cm-1.

When the density of the product was measured, it was found to be 1.25.
9, and the volumetric expansion coefficient calculated from the density of the monomer is 4.
．． It was 5%.

Reference Example 2 Spiro[1,5-dihydro-5'-methylene-2,4-
spiro[1,5] obtained in Example 2 in place of 248 mg of benzodioxepine-3,2'-[1,3]dioxepane]
-dihydro-2,4-benzodioxepine-5'-methylene-4',6',7'-trimethyl-3,2'-[1
, 3] Dioxepane] Polymerization was carried out in the same manner as in Reference Example 1 except that 290 mg of dioxepane was used to obtain a polymer having a number average molecular weight of 1540 and a molecular weight distribution of 1.88. The volumetric expansion rate from the monomer was 4.7%.

Reference Example 3 Spiro[1,5-dihydro-5'-methylene-2,4-
spiro[7-chloro-1,5-dihydro-5'-methylene-2,4-benzodioxepane] obtained in Example 3 in place of 248 mg of benzodioxepine-3,2'-[1,3]dioxepane] Polymerization was carried out in the same manner as in Reference Example 1 except that 283 mg of xepin-3,2'-[1,3]dioxepane was used to obtain a polymer having a number average molecular weight of 2010 and a molecular weight distribution of 2.01. Volumetric expansion rate from monomer is 5.1%
Met.

Reference Example 4 Spiro[1,5-dihydro-5'-methylene-2,4-
Spiro[1,5-dihydro-5
'-Methylene-2,4-benzodioxepine-3,2'
Reference Example 1 except that a mixture of 124 mg of [1,3]dioxepane] and 50 mg of methyl methacrylate was used.
Polymerization was carried out in the same manner as above to obtain a polymer having a number average molecular weight of 3670 and a molecular weight distribution of 1.99. The volumetric expansion rate from the monomer was -1.5%.

[0072]

According to the method of the present invention, a spiro-orthocarbonate compound which undergoes not only cationic ring-opening isomerization polymerization but also radical ring-opening isomerization polymerization and exhibits volume expansion is provided.

[Brief explanation of the drawing]

FIG. 1: 1H-N of a precursor of an example of a compound according to the invention.
It is a figure showing an MR spectrum.

FIG. 2 shows an IR spectrum of a precursor of an example of a compound according to the invention.

FIG. 3 shows a 1H-NMR spectrum of an example of a compound according to the invention.

FIG. 4 shows an IR spectrum of an example of a compound according to the invention.

Claims (1)

[Claims] [Claim 1] The following chemical formula 1 [Chemical 1] (wherein R1, R2, R3, R4, R5, R6, R7,
R8, R9, R10, R11 and R12 each represent a hydrogen atom or a lower alkyl group, R13, R14, R1
5 and R16 are each a hydrogen atom, a lower alkyl group,
Alkyloxy group, halogen group, nitro group, cyano group,
Represents an amino group, amide group, hydroxyl group or ester group. ) is a spiro-orthocarbonate compound.