JPH0455194B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula, the following general formula (1) (However, R ₁ is a hydrogen atom or an alkyl group, R ₂ is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and n is an integer of 1 to 4.) Conventionally, compounds having a 2,6,7-trioxysabicyclo[2,2,2]octane group (hereinafter referred to as
Abbreviated as bicyclo compound. ) have been investigated for use as stabilizers for vinyl chloride resins, herbicides, etc. Recently, ring-opening isomerization polymerization of this type of compound has been investigated, and a unique phenomenon in which the volume change accompanying polymerization is extremely small has been reported. It is attracting attention for its use in materials and adhesives. In recent years, progress has been made in developing polymers having this 2,6,7-trioxabicyclo[2,2,2]octane group (hereinafter abbreviated as bicyclo group) in its side chain. Such a polymer dissolved in an appropriate solvent undergoes ring-opening isomerization of the bicyclo group in the side chain using a ring-opening isomerizing agent or ultraviolet rays, and becomes crosslinked and insolubilized. Therefore, the application of such polymers having bicyclo groups in their side chains to paints, adhesives, photoresists, etc. is being considered. The following are known as bicyclo compounds that yield polymers having bicyclo groups in their side chains. (However, R is a hydrogen atom or an alkyl group.) However, among the above bicyclo compounds, (2) and (3)
During radical polymerization of the vinyl group of the bicyclo compound, insolubilization tends to occur due to crosslinking due to ring-opening isomerization of the bicyclo group in the side chain, and storage of the polymer having a bicyclo group in the side chain obtained by radical polymerization is difficult. There are problems such as poor stability. Furthermore, the above bicyclo compound (4) has the problem that ring-opening isomerization of the bicyclo group occurs as a side reaction during polymerization of the bicyclo compound (Chemical Society of Japan, Proceedings of the 49th Spring Annual Meeting, 1229 (1984)). Therefore, the present inventors developed a bicyclo compound that does not have the above-mentioned problems, that is, a bicyclo compound that does not involve crosslinking or ring opening of the bicyclo group during radical polymerization of the vinyl group.
We have continued to develop bicyclo compounds containing vinyl groups, which produce polymers with good storage stability. As a result, the inventors discovered that a bicyclo compound having a specific structure could satisfy the above conditions, and completed the present invention. That is, the present invention provides the following general formula (1) (However, R ₁ is a hydrogen atom or an alkyl group, R ₂ is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and n is an integer of 1 to 4.) . In the general formula (1), the alkyl groups represented by R ₁ and R ₂ are not particularly limited in the number of carbon atoms,
Various types are used. However, in general, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl groups, are particularly preferred because of the ease of obtaining raw materials. In addition, in the general formula (1), the hydroxyalkyl group represented by R ₂ is not particularly limited in its carbon number, and various types can be used, but it generally has 1 to 1 carbon atoms due to the ease of obtaining raw materials. 4 is preferred. In general, preferred hydroxyalkyl groups in the present invention include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. Furthermore, in the general formula (1), when the value of n is small, rectification for isolating the bicycloorthoester compound of the present invention can be relatively easily carried out after the synthesis reaction of the bicycloorthoester compound. . Therefore, compounds in which n is 1 are the most preferred compounds from the standpoint of isolation operations after the synthesis reaction. The bicycloorthoester compound of the present invention is a colorless transparent crystal or a colorless transparent liquid at room temperature,
Crystallinity tends to improve as the number of carbon atoms in R ₁ and R ₂ decreases. In addition, the bicycloorthoester compound includes carbon tetrachloride, chloroform, methylene chloride, acetone, hexane, benzene, toluene,
Soluble in tetrahydrofuran, dioxane, etc. The bicycloorthoester compound of the present invention can be confirmed to be such a compound by the following measurements. (1) Measurement of infrared absorption spectrum (IR) Bicyclo group

[Formula] and the presence of a double bond (-C=C-) can be confirmed. Several absorption bands originating from the former appear between 1100 and 900 cm ^-1 , and absorption bands originating from the latter appear between 1600 and 900 cm -1.
One appears at 1680cm ^-1 . (2) ¹ H− nuclear magnetic resonance absorption spectrum ( ¹ H−
NMR) measurement When measured in deuterated chloroform solvent with tetramethylsilane as the standard, δ (ppm) = 3.8 to 4.1
A singlet absorption peak derived from the six methylene hydrogens in the bicyclo group appears at the position. or,
A multiplet absorption peak originating from hydrogen in the double bond structure appears at a position of δ (ppm) = 4.7 to 6.5. Furthermore, the absorption peak derived from the alkylene hydrogen between the double bond and the bicyclo group is, for example, n
When = 1, a double line appears at δ (ppm) = 2.3 to 2.6. (3) Mass spectrometry (MS) Molecular weight can be confirmed by using electron impact method (EI method) and electrolytic desorption method (FD method) as mass spectrometry. When the molecular weight of the compound is M, the molecular ion peak is at the position m/e=M ⁺ ,
Alternatively, a pseudomolecular ion peak is observed at the (M±1) ⁺ position. (4) Elemental analysis This can be confirmed by comparing the analysis results of carbon and hydrogen with the theoretical values calculated from the above general formula (1). The bicycloorthoester compound of the present invention can be confirmed by the various measuring methods described above. The method for producing the bicycloorthoester compound represented by the general formula (1) is not particularly limited, and any method may be employed. Examples of generally industrially suitable methods are as follows. That is, general formula (5) (However, R ₁ is a hydrogen atom or an alkyl group, R ₂ is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and n is an integer of 1 to 4.) By carrying out the following steps, a bicycloorthoester compound represented by the above general formula (1) can be produced. The reaction formula is shown in the above formula (5), where R ₁ is a hydrogen atom,
The compound where n=1 is shown below. In the dehydrobromation reaction, any known dehydrogenating agent may be used without any restriction. Suitably used dehydroborizing agents include alkali metal alkoxides. Among others, potassium-t-
Potassium alkoxides such as butoxide and potassium-isopropoxide are preferred. The charging ratio of the bicyclo compound represented by the general formula (5) and the dehydrogenating agent is preferably equimolar, or the dehydrobromating agent is preferably used in an excess of about 1.5 times by mole at most. The dehydrobromination reaction of the bicyclo compound represented by the general formula (5) may be carried out by dissolving it in an appropriate solvent such as tetrahydrofuran. The temperature of the above reaction may range from room temperature to the boiling point of the solvent, preferably from 50°C to the boiling point of the solvent. After the dehydrobromination reaction, the generated salt is separated,
Subsequently, the reaction solution is concentrated and distilled under reduced pressure to obtain a mixture of the bicycloorthoester compound of the present invention and the bicyclo compound produced by the side reaction. Further, by rectifying this mixture, the bicycloorthoester compound represented by the general formula (1) of the present invention is isolated. The bicycloorthoester compound represented by the general formula (1) of the present invention is a compound having both a bicyclo group and a vinyl group, and an alkylene group between both groups. Bicycloorthoester compound (1) of the present invention
performs addition polymerization of vinyl groups using a radical polymerization initiator, has few side reactions such as ring-opening isomerization of bicyclo groups in both bulk and solution polymerization methods, and is soluble in various solvents and stored. Provides a polymer with good stability. Examples of the radical polymerization initiator include organic peroxides such as t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, and benzoyl peroxide, azobisisobityronitrile, and azobiscyclohexane. Asobis-based initiators such as carbonitrile are preferably used. In addition, the amount of initiator used is 0.1 per bicycloorthoester compound (1).
It may be used in the range of ~20 mol %, and generally, the larger the amount of initiator, the higher the polymerization rate and the lower the ring-opening isomerization rate. Furthermore, polymerization is performed from 0℃ to 200℃ from reduced pressure to increased pressure.
Although the reaction can be carried out under any conditions up to 100° C., it is preferably carried out at a temperature of 50 to 150° C. under pressure near normal pressure. As the solvent used in the above solution polymerization, any known organic solvent can be used without any restriction as long as it is inert to the bicycloorthoester compound (1), but specific examples include benzene, toluene, etc. , xylene, chlorobenzene, dioxane, tetrahydrofuran, dimethylformamide, diethylacetamide and the like are preferably used. The polymer produced by radical polymerization of the bicycloorthoester compound of the present invention and having a bicyclo group in the side chain is in the form of a white powder and is soluble in chloroform, methylene chloride, acetone, tetrahydrofuran, dioxane, and the like. Further, it was found from the infrared absorption spectrum of the above polymer that the ring-opening isomerization rate of the bicyclo group was only 3% or less. In the case of the following bicyclo compound (7) which has a structure similar to the bicycloorthoester compound of the present invention and is a known compound (However, R is an alkyl group.) The ring-opening isomerization rate accompanying radical polymerization reaches about 6%. An increase in the ring-opening isomerization rate not only causes a loss of bicyclo groups, but also causes insolubilization due to crosslinking of the polymer, which significantly deteriorates the subsequent operability of the resulting polymer. Therefore, it is clear that the bicycloorthoester compound (1) of the present invention is a compound that is greatly improved in the above points over known compounds. However, the value of the ring-opening isomerization rate shown here is a value determined by the following method. In other words, when a bicyclo compound undergoes ring-opening isomerization, it produces an ester, so the following two model compounds were selected. These were mixed at a predetermined ratio, a calibration curve was prepared using the absorbance of the ester on the infrared absorption spectrum of the mixture, and the calculation was made from this calibration curve. Moreover, the bicycloorthoester compound (1) of the present invention
can be easily copolymerized with other vinyl group-containing compounds. As the above vinyl group-containing compound,
Generally known ethylenically unsaturated compounds can be used without any restrictions, but specific examples include acrylonitrile, vinyl acetate, maleic anhydride, styrene, methyl acrylate, ethyl acrylate,
Examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Furthermore, the bicycloorthoester compound of the present invention
In (1), a cationic ring-opening isomerization polymerization of a bicyclo group can be carried out using a cationic polymerization catalyst. As the cationic polymerization catalyst, in addition to Lewis acids such as boron trifluoride, boron trifluoride, ether complexes, boron trifluoride amine complexes, polymerization means using ultraviolet rays, X-rays, electron beams, etc. can be employed. Examples of cationic polymerization catalysts for ultraviolet polymerization include aromatic diazonium salts, aromatic halonium salts, aromatic onium salts, and the like. The amount of the cationic polymerization catalyst used is usually 0.01 to 15 wt%, and the polymerization temperature is -80 to 250°C, preferably 0 to 200°C. As described above, the bicycloorthoester compound of the present invention is a compound having both a vinyl group and a bicyclo group in one molecule. Therefore, both radical polymerization of vinyl groups and cationic ring-opening isomerization polymerization of bicyclo groups can be carried out. Moreover, because an alkylene group exists between the vinyl group and the bicyclo group, the ring-opening isomerization rate of the bicyclo group in the polymer produced by radical polymerization is about half that of conventionally known bicyclo compounds. It is possible to obtain a purer polymer with less amount. Furthermore, it has the characteristic that insolubilization due to crosslinking does not occur during polymerization. Therefore, the bicycloorthoester compound of the present invention is the most suitable monomer for obtaining a polymer having a bicyclo group in the side chain, which is purer, soluble, and has excellent storage stability, and is suitable for industrial applications such as photoresists. It is a particularly useful material as a raw material for various purposes. In addition, by utilizing the non-shrinkage property in ring-opening isomerization polymerization of bicyclo groups, it can be applied to various industrial applications such as sealing materials, molding materials, casting materials, adhesives, and paints. I can do it. Reference Examples, Examples, and Comparative Examples are given below to further specifically explain the present invention, but the present invention is not limited to these Examples. Example 1 A 200c.c. dropping funnel and reflux condenser were installed.
22.4 g (0.20 mol) of potassium t-butoxide and dry tetrahydrofuran in a 300 c.c. two-necked flask.
150 c.c. was taken and potassium t-butoxide was dissolved under stirring. Then 1-(1-bromopropyl)-4
A solution of 49 g (0.185 mol) of -ethyl-2,6,7-trioxabicyclo[2,2,2]octane dissolved in 50 c.c. of dry tetrahydrofuran was added dropwise from the dropping funnel over about 1 hour. After the dropwise addition was completed, heating was started to reflux the tetrahydrofuran. After 5 hours, the reflux was stopped and the mixture was allowed to cool. After cooling,
The reaction solution was filtered, and the filtrate was concentrated. Next, perform vacuum distillation to obtain a fraction of 73-90℃/0.65mmHg.
67.8℃/0.70mm by further repeating vacuum distillation
3.11 g of Hg fraction was obtained. The yield was 9.1%.
Various measurements of the product thus obtained were as follows. (1) Boiling point 67.8℃/0.70mmHg (2) Infrared absorption spectrum (results are attached as Figure 1) 1645cm ^-1 (CH ₂ =CH-) 1060, 1000,

[Formula] (3) ¹ H-Nuclear Magnetic Resonance Absorption Spectrum (The results are attached as Figure 2) Measurement solvent: Deuterochloroform Standard: Tetramethylsilane

[Table] (4) Mass spectrometry (FD method) m/e=184 (M ⁺ )

[Table] From the above various measurement results, the structural formula of the product is 1-allyl-4-ethyl-2,6,7 represented by
- It was confirmed that it was trioxabicyclo[2,2,2]octane. Example 2 200c.c. Adding funnel and reflux condenser installed
18 g (0.161 mol) of potassium t-butoxide and 150 cc of dry tetrahydrofuran were placed in a 300 c.c. two-necked flask, and the potassium t-butoxide was dissolved under stirring. Then 1-(1-bromopropyl)
A solution of 38 g (0.151 mol) of -4-methyl-2,6,7-trioxabicyclo[2,2,2]octane dissolved in 50 c.c. of dry tetrahydrofuran was added dropwise from the dropping funnel. Thereafter, the same operation as in Example 1 was carried out, and 1-allyl-4-methyl-2,6,7-trioxabicyclo[2,
2,2]octane was obtained in a yield of 5.5%. The above-mentioned bicyclo compound was confirmed by the measuring method described above. That is, the presence of a bicyclo group was confirmed by the infrared absorption spectrum and ^{the 1} H-nuclear magnetic resonance absorption spectrum (the results are attached as Figure 3), and the mass spectrometry revealed that m/e = 170.
A molecular ion peak of (M ⁺ ) was confirmed. In addition, the results of elemental analysis were as shown in Table 3.

[Table] Examples 3 and 4 As raw materials, 1-(1-bromopropyl)-2,
Except for using 6,7-trioxabicyclo[2,2,2]octane and 1-(1-bromopropyl)-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane All operations were performed in the same manner as in Example 1, and the products shown in Table 4 were synthesized. The yields were 15.1% and 12%, respectively. The product was confirmed by various measuring methods as described above. That is, the presence of a bicyclo group was confirmed by infrared absorption spectrum and ¹ H-nuclear magnetic resonance absorption spectrum, and the results of mass spectrometry and elemental analysis are shown in Table 4.

[Table] Reference Example 1 and Comparative Example 1 1-allyl-4-ethyl- produced in Example 1
2,6,7-trioxabicyclo[2,2,2]
Take 0.5111g of octane in an ampoule and add
40.6 mg of t-butyl peroxide (10 mol % vs. bicyclo compound) was added. The ampoule was cooled in dry ice-methanol, the pressure was reduced using a vacuum pump, and the tube was sealed. Next, this sealed ampoule was polymerized in a 120°C oil bath for 24 hours.
The ampoule was then broken and the contents dissolved in about 1 c.c. of methylene chloride and then precipitated into hexane.
The precipitated polymer was obtained as a white powder by filtration and drying, and the polymerization rate was 53.8%. The result of measuring the infrared absorption spectrum of this polymer was 1720
A slight absorption of the ester was observed at cm ^-1 , and the absorbance value of the ester absorption corresponded to a ring-opening isomerization rate of 2.4% from the above-mentioned calibration curve. As a comparative example, 1-vinyl-4-ethyl-2,
Using 6,7-trioxysabicyclo[2,2,2]octane, 10 mol% of di-t-butyl peroxide was added and polymerization was carried out at 120°C for 24 hours in the same manner as above. As a result, a white powdery polymer was obtained, and its ring-opening isomerization rate was 5.2%. In addition, the polymer produced in Reference Example 1 showed no change in solubility even after two months at room temperature and indoor humidity, and no change was observed in the absorption of bicyclo groups in the infrared absorption spectrum. Ta. Comparative Example 2 Approximately 0.5 g of 1-ethyl-4-methacryloyloxymethyl-2,6,7-trioxabicyclo[2,2,2]octane represented by the following formula was placed in an ampoule, and then the Initiator and solvent as indicated were added. Subsequently, the ampoule was sealed while cooling in dry ice-metal. After sealing the tube,
The ampoules were polymerized in an oil bath under the conditions shown in Table 5. The results are also listed in Table-5.

[Table] Furthermore, the soluble polymer produced in No. 3 became insolubilized after one month at room temperature and indoor humidity. Reference Example 2 The bicyclo compounds of the present invention produced in Examples 2, 3, and 4 were taken into an ampoule in the same manner as in Reference Example 1, 10 mol% of di-t-butyl peroxide was added, and the mixture was cooled in dry ice methanol. The tube was sealed under reduced pressure. Next, this sealed ampoule was polymerized in an oil bath at 120°C for 24 hours. The treatment after polymerization was carried out in the same manner as in Reference Example 1. The obtained polymer was in the form of a white powder, and its ring-opening isomerization rate was as shown in Table 6.

【table】 [Brief explanation of drawings]

1 and 2 show the infrared absorption spectrum and ¹ H-nuclear magnetic resonance absorption spectrum of the bicyclo compound obtained in Example 1. FIG. 3 shows the ¹ H-nuclear magnetic resonance absorption spectrum of the bicyclo compound obtained in Example 2.

Claims (1)

[Claims] 1. General formula (However, R ₁ is a hydrogen atom or an alkyl group, R ₂ is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and n is an integer of 1 to 4.) A bicycloorthoester compound represented by the following.