JPS59155384A - Methylene group-containing spiro ortho-carbonate compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I . EXAMPLE:2-Methylene-1,4,6,9-tetraoxaspiro[4,4]nonane and a 2-alkyl-7-methylene- 1,4,6,9-tetraoxaspiro[4,4]nonane. USE:A polymerizable monomer. Useful as a raw material for a molding material, adhesive, coating compound, etc. Easily obtainable by using an inexpensive raw material. PREPARATION:A compound shown by the formula II is reacted with 1.1-5 times the molar quantity of an alkali(e.g., sodium alcoholate, etc.) in a solvent such as N,N-dimethylformamide, pyridine, etc. at 0-60 deg.C, and dehydrohalogenated to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel compound of 2-methylene-1,4,6
, 9-tetraoxaspiro[4,4)nonane and 2-
Alkyl-7-methylene-1,4,6,9-tetraoxaspiro[4,41 nonane (hereinafter referred to as compound [1])
Compound [1] has the following formula [
1] and is useful as a polymerizable monomer, for example.

(Here, R represents a hydrogen atom or an alkyl group.) Compound [1] is 2-no-rogenated methyl-1,4,6,9-tetraoxaspiro(4,4
] Deno-logenation of nonane and 2-alkyl-7-no-logenated methyl-1,4,6,9-tetraoxaspiro(4,4) nonane (hereinafter collectively referred to as compound [2]) Produced by hydrogen reaction.

(Here, R represents a hydrogen atom or an alkyl group, and X represents C
Indicates a halogen atom such as I, Br, I. The same shall apply hereinafter. ) This reaction is shown below.

[2] [1] Compound [2] is 1,6-thioxolane-2-one, 4-
By addition reaction between substituted and unsubstituted ethylene carbonates (cyclic carbonates) such as methyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, etc. and shrimp 710 hydrin. can be manufactured. This reaction formula is shown below: In the production of compound [2], epino-rohydrin and cyclic carbonates are mixed with an acid such as BF30Et in a solvent such as methylene chloride or tetrahydrofuran.
2.5nC14, TiC1,, FeCl3, P-t/l
Z! - The reaction is carried out using an acid such as sulfonic acid or sulfuric acid as a catalyst. The reaction temperature is not particularly limited, but is generally carried out at 0°C to 60°C. In addition, there are no particular restrictions on the molar ratio of epihalohydrin/cyclic carbonate, the catalyst concentration, and the amount of solvent used, but in general, epihalohydrin/cyclic carbonate
Molar ratio of cyclic carbonate = 0.6 to 1.5, catalyst concentration 0.1 to 3 wt% (weight ratio of charged cyclic carbonate),
The amount of solvent used is 0.5 to 20 (weight ratio to cyclic carbonate charged).

The degree of regression of the reaction can be determined by measuring the reaction solution using, for example, a gas chromatograph (
It can be easily determined by analysis using GC (abbreviated as GC) or liquid chromatography (abbreviated as HLC).

Compound [2] is separated and obtained from the reaction solution as follows. For example, an alkaline aqueous solution such as a sodium hydroxide aqueous solution is added to the reaction solution while cooling it with ice water, and the mixture is stirred and separated into an aqueous layer and an organic layer.

The organic layer is then washed with 10% NaCl aqueous solution. Next, after dehydrating the organic layer with magnesium sulfate, low-boiling substances are first removed by atmospheric distillation, and the residue is distilled under reduced pressure to obtain compound [2].

Compound [1] is synthesized by mixing compound [2] in a suitable solvent such as N,N-dimethylformamide, pyridine, etc. in a theoretical amount or an excess amount, preferably 1.1
This is carried out by dehydrohalogenation by reaction with an alkali such as sodium alcolade in a molar amount of ~5 times.

□ There is no particular restriction on the reaction temperature, but it is generally between 0°C and 60°C.
It is carried out at ℃.

Further, the degree of progress of the reaction can be easily determined by analyzing the reaction solution using, for example, a gas chromatograph or a liquid chromatograph (abbreviated as HLC).

Compound [1] can be separated from the reaction solution by, for example, pouring the reaction solution into water, separating the organic layer and the aqueous layer, and then adding ether,
Contains chloroform, toluene, etc.5! This can be carried out by performing an extraction operation on the aqueous layer with a medium, combining the extracted layer and the organic layer, dehydrating and drying, distilling off the solvent, and distilling the residue under reduced pressure.

Regarding radically polymerizable spiroorthocarbonates, see Endo T., and Balley W. J.
,,J.

Polym, Sci, Polym, Chem,
Ed., 13, 2525 (1975), etc. However, these compounds have the property that the spiroorthocarbonate ring opens during radical polymerization. Moreover, the synthesis method for these spiroorthocarbonates is complicated and requires the use of C8l, which has a low boiling point and is harmful, and expensive raw materials, making it difficult to manufacture and making the desired product expensive. It has its drawbacks.

On the other hand, as a result of intensive research, the present inventors have found that the compound not only undergoes cationic ring-opening polymerization, but also undergoes radical polymerization without ring-opening of the spiro-orthocarbonate ring, which is a property different from that of the above-mentioned known compounds. They have discovered a compound [1] that has the following properties.

Moreover, the compound [1] of the present invention has the advantage that it can be easily synthesized by a simple reaction of dehydrohalogenation using the compound [2] synthesized from inexpensive epihalohydrin and a cyclic carbonate, which are generally commercially available, as raw materials. .

The radical polymerization of compound [1] is as follows.

A polymer having a spiroorthocarbonate ring is obtained by radical polymerization.

In addition, compound [1,] undergoes cationic polymerization using a cationic polymerization initiator, and at this time, the spiroorthocarbonate ring opens to form a carbonate bond, and a part of the cyclic carbonate compound also undergoes an elimination reaction, resulting in a viscous structure. Gives a polymer.

As mentioned above, the compound [1] of the present invention can be easily and inexpensively produced, and can be polymerized by either radical polymerization or cationic polymerization, and the polymer has a number of molecules in its main chain. It has a carbonate group or a spiroorthocarbonate ring in its side chain. Therefore, the compound [1] of the present invention is an extremely useful compound as a raw material for molding materials, adhesives, paints, etc.

Radical polymerization of compound [1] can be carried out by conventional radical polymerization means, such as ultraviolet rays, infrared rays, heat, electron beams, or microwaves.

In ultraviolet radical polymerization, a photoinitiator is usually used.

Photoinitiators that can be suitably used include acetophenone,
2,2-dimethoxy-2-phenylacetophenone, 2
, 2-di-earthoxyacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-
Hydroxy-2-methylpropiophenone, 4.4'-
Bis(diethylamino)benzophenone, benzophenone, methyl-(0-benzoyl)-benzoate, 1-
Phenyl #-1,2-propanedione-2-(0-ethoxycarbonyl)-oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl)-oxime, benzoin, benzoinmethylni□thyl, Carbonyl compounds such as benzine ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl or diacetyl; methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone or 2-i-
Anthraquinone or xanthone derivatives such as propylthioxanthone; sulfur compounds such as diphenyl sulfide, diphenyl disulfide or dithiocarbamates; α-
Examples include chloromethylnaphthalene and antho2cene.

In the polymerization using infrared rays, heat, or microwaves, any radical initiator can be used as long as it can generate radicals by decomposition. For example, Jeter
t-Butyl peroxide, 2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, t
ert-butylhydrono-oxide, tert-
Organic peroxides such as butyl peroxydipenzoate; 2,
Azo compounds such as 2'-azobisisobutyronitrile; persalts such as ammonium persulfate and potassium persulfate can be used.

Further, polymerization using ionizing radiation such as an electron beam is usually carried out without a catalyst.

When a catalyst is used, the amount used is generally 0.01 to 10 wt%, preferably 0.1 to 5 wt% based on the total amount of monomers.
The range is wt%.

Radical polymerization proceeds even at room temperature when irradiated with ultraviolet rays or ionizing radiation, but in other cases it proceeds smoothly under heating or heating conditions. When a solvent is used during polymerization, examples of preferably used solvents include toluene, xylene, ethyl acetate, N,N-dimethylformamide, chloroform, and dioxane. Further, the cationic polymerization of compound [1] is carried out by a generally well-known method, that is, by using, for example, ultraviolet rays, infrared rays, heat, or microwaves in the presence of a cationic polymerization initiator.

As a cationic polymerization catalyst in the case of ultraviolet irradiation, for example, φ-M2N-PF6. Aromatic diazonium salts such as φ-N Sanshoku, Bku, etc.Aromatic diazonium salts such as φ-■-φ・PF7 etc.
Ronium salt; 1 CH.

Aromatic onium salts of group Va elements of the periodic table, such as; aromatic onium salts of group elements; dicarbonyl complex compounds of group Va elements;

In addition, other cationic polymerization catalysts include, for example, BF
s, FeC13,5nC1,, SbF3. Ti1
Lewis acids such as BF30Et2. Lewis acids such as BF3-aniline complex and 0. S,
Coordination compounds with compounds having N, etc.; oxonium salts, diazonium salts, carbonium salts of Lewis acids;)-halogen compounds, mixed halogen compounds, perhalogen acid derivatives, and the like.

The amount of catalyst used is generally based on the monomer to be polymerized.
0.001-10wt% preferably 0.1-5wt%
A range of is suitable. Although there are no particular restrictions regarding the polymerization temperature, it is usually carried out at room temperature to 200°C.

When using a solvent during polymerization, it is desirable to choose a compound that does not react with the growing cation and reduce its activity. Suitable solvents for use include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride, 1,1-dichloroethane, and others.

Example 1 In a fourth 500 d flask equipped with a stirrer, condenser, thermometer and addition funnel, sodium methylate 2
1.6.9 (0.4 mol) and 150 wLt of N,N-dimethylformamide were added, and 7-
Chloromethyl-2-methyl-1,4,6,9-tetraoxaspiro(4,4)nonane 3B, 911 (0.2 mol) was added dropwise over 1 hour. During this time, the reaction solution was kept at about 15°C. Thereafter, the mixture was reacted at 50° C. for 6 hours and left overnight.

Next, the reaction solution was poured into 300 m of water, and the aqueous layer and organic layer were separated. Next, the operation of adding 100 ml of methylene chloride to the aqueous layer for extraction was repeated 6 times, and each methylene chloride layer was combined with the organic layer and washed with 100 ml of water. This was dehydrated with magnesium sulfate, solvent removed using a rotary evaporator, and then distilled under reduced pressure to obtain 2-methyl-7-methylene-1,4,6,9-tetraoxaspiro (4 , 411 nona 722.9 g (yield 7
2%).

Its physical property values are as follows.

O specific gravity; 1.170 (25°C) 0 boiling point; 79°C/4,8 H11 0 infrared absorption spectrum (hereinafter abbreviated as ■R); (1st
(See figure) 1 703cIIL (CH2C) 1222cx, 1030clL (C-0-C)
0 nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR) (C
DCl, medium); (see Figure 2) δ (ppm) 4.4-4.8 (4H,CH,=C,CH2-0)3
．． 5-4.4 (3H,0-CH-CH2-0)1.2
~1.5 (3H, -CH,) OGC-MS; Parent P (m/e); 158 -7-chloromethyl-2-methyl- used above
1,4,6,9-tetraoxaspiro[4,4)nonane was produced by the following method.

i.e. 4-neck II with stirrer, condenser, thermometer and dropping funnel! 20' methylene chloride in flask
ON! , 4-methyl-1,5-dioxolan-2-one 40.8.9 (0.4 mol) was taken, and about 2
After cooling to 5°C and adding BF30E t2o,4 d, add epichlorohydrin 44.4.9 (0,4
8 mol) dissolved in 200 methylene chloride, about 1
It dripped over time. The mixture was further reacted at about 25° C. for 4 hours. Next, 0.8 m of triethylamine was added to deactivate the catalyst.

The reaction solution was washed once with 200 ml of 8% NaOH aqueous solution, and the organic layer was washed twice with distilled water SO= and then dehydrated with Mg SO.

Next, the solution was removed and distilled under reduced pressure using a KO-1 evaporator. Boiling point 96-95℃ / 7 at 1.5 mmHll
-Chloromethyl-2-methyl-1,4,6,9-tetraoxaspiro[4,43nonane 2t 69 (yield 2
8%).

Its physical property values are as follows.

0 boiling point; 96~boIR; (see Figure 6) 1243cm, 1055cm (C-0-C)ON
MR; (CDCI, middle) (see Figure 4) δ (ppm) 6.8 to 4.6 (5) 3 of L2CH-0, CH2-0
H) 6.4-5.8 (5...CH, -CI, 1H of C-O) 1.2-1.5 (3I upper d, OCH3') CxC-M
S; Parent peak; P -1 = 193 (m/e) Reference example 1 2-methyl-7-methylene-1,4,6 obtained in Example 1
, 9-tetraoxaspiro C4,4''J nonane was added with 6 mol % of di-tert-butyl-butyl oxide as a polymerization catalyst, and a polymerization reaction was carried out at 130° C. for 40 hours in a sealed tube.

This polymer was fractionated under the following separation conditions, and the polymer component was fractionated as a polymer.

Separation conditions: Equipment: HLC-807 column manufactured by Toyo Soda Kogyo ■; TS
K-GE# G-30,0OH (3+G2000HG eluent; chloroform flow rate; 4 d/min) The obtained polymer was a light yellow powdery substance, and the yield was about 80%.

According to HLC analysis, the weight average molecular weight of the polymer was 6,800 in terms of polystyrene.

In addition, IR analysis of the polymer revealed that 1703clIL (
The peak of C=CH2) disappeared, and the peak of 1240c11V1.
1210cm, 1045cm ノ(C-0-c
) peaks were observed (see Figure 5).

In the above radical polymerization, 2-methylene-7-mef
Roux 1, 4. The methylene group of be9-tetraoxaspiro[4,4)nonane was polymerized and its spiro-orthocarbonate group was not ring-opened, so this polymer contained a spiro-orthocarbonate group. . The specific gravity of this polymer is 1290 (25° C.), and the volume shrinkage rate during polymerization calculated from this value is 96%.

Reference example 2 2-methyl-7-methylene-1,4,6 obtained in Example 1
,9-TetraoxaspiroC4,4]nonane was placed in a glass test tube, cooled to about 10°C with ice water, and then BP, OE
t, was added in an amount of 6 mol % and polymerized.

As a result, a dark and viscous polymer was produced.

4-methyl-1,3-dioxolan-2-one was found in this polymer component.

Further, the polymer component was fractionated in the same manner as in Reference Example 1, and a dark brown solid polymer was obtained with a yield of 4°0%.

According to HLC analysis, the weight average molecular weight of the polymer was 2,200 in terms of polystyrene.

In addition, a (C=O) peak at 1730cIrL was observed by IR analysis.

By the above cationic polymerization, 2-methyl-7-methiney-1,4,6,9-tetraoxaspiro[4,4]
Nonane has its spiroorthocarbonate group ring-opened,
Carbonate groups were generated in the polymer.

Reference Example 6 Adding benzoin ethyl ether to the compound obtained in Example 1 for 5
wt%, and sandwiched between Mylar films to a thickness of about 80 μm, irradiated with ultraviolet rays at a height of 20 cm for 8 minutes using an 80 W/am high-pressure mercury lamp manufactured by Ushio Inc., to combine one ultraviolet radical.

HLC analysis of the irradiated material confirmed the formation of a polymer.

Reference Example 4 The polymer obtained in Reference Example 1 was dissolved in about 20 times the weight of 1,1-dichloroethane, and 3 wt% of BF30Et was added to the polymer, resulting in crosslinking and precipitation of the polymer.

[Brief explanation of drawings]

Figure 1 shows 2-methyl-7-methylene-1 obtained in Example 1.
, 4,6,9-tetraoxaspiro[4,4:)nonane, and Figure 2 shows the NMR spectrum of the same compound.
Fig. 3 is a spectrum diagram of 7- which is an intermediate raw material.
FIG. 4 is an IR spectrum diagram of chloromethyl-2-methyl-1,4,6,9-tetraoxaspiro[4,4)nonane; FIG. 4 is an NMR spectrum of the same compound;
The figure shows 2-methyl-7-methylene-1,4 obtained in Reference Example 1.
, 6,9-tetraoxaspiro[4,4]nonane radical polymer. Name of patent applicant Toagosei Kagaku Kogyo Co., Ltd. Procedural Amendment 1982 Mezuki-? Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 26304 of 1982, Name of the invention, Methylene group-containing spiro-orthocarbonate compound3, Relationship with the person making the amendment, Patent applicant's address, Tokyo 1-14-1-4 Nishi-Shinbashi, Miyakominato-ku, Column 5 of the detailed description of the invention in the specification to be amended, Contents of the amendment (1) Page 5 of the specification, lines 12-14, 64 “Gas black thorn rough or liquid Chromatograph (abbreviated as HLC)" is corrected to rGC or HLCJ. (2) r13 on page 6, line 4 of the specification. It says “J” “Top 3.
Correct with J. (4) On page 16, line 2 of the specification, r O-CH, J is corrected to r C-, CH, J. that's all

Claims (1)

[Claims] 16. A spiro-ortcarbonate compound represented by the following formula [1]. (R represents a hydrogen atom or an alkyl group here.)