JPH0469627B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an azo bond-containing acrylic ester compound which is a new substance. This azo bond-containing acrylic ester compound and the polymer obtained by polymerizing it are said to be particularly useful as a stationary phase for separation in gas chromatography, and have excellent properties as a liquid crystal (nematic liquid crystal). (Prior Art) Many stationary phases for glass chromatography are already known, such as various phthalate esters and liquid paraffin. but,
No substance has yet been developed as the stationary phase that exhibits satisfactory performance in mutually separating specific compounds with relatively large molecular weights having close boiling points, isomers of pheromone substances, and the like. (Structure of the Invention) The present inventors have repeatedly conducted synthetic research regarding the above technical problem, and as a result of detailed analysis and testing, the following general formula We have successfully developed a new azo bond-containing acrylic acid ester compound. R ¹ in the general formula () represents a hydrogen atom or a methyl group. Also, R ² is the formula C _n H _2n+1 or OC _n
A group represented by H _2n+1 (where m is an integer of 1 to 4),
That is, it is a lower alkyl group or alkoxy group selected from a methyl group, an ethyl group, a propyl group, a butyl group, and a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The azo bond-containing acrylic ester compound represented by the above general formula () provided by the present invention has the following formula: An acid chloride compound having an acryloyl group represented by and the following general formula (R ³ and R ² are as described above) It is synthesized by dehydrochlorinating an azo compound represented by the following in the presence of a hydrogen chloride scavenger such as triethylamine. In the reaction, it is desirable to use approximately the same mole of the azo compound of the general formula () per mole of the acid chloride compound of the formula ().
Note that the product is purified by washing and recrystallization. The acid chloride compound having an acryloyl group of the above formula () can be produced from thionyl chloride using p-hydroxybenzoic acid, 2-chloroethanol and acrylic acid as raw materials. That is, after adding potassium hydroxide and potassium iodide to 4-hydroxybenzoic acid in an ethanol-water system, 2
- Reaction with chloroethanol to obtain 4-(2-hydroxyethoxy)benzoic acid, which was reacted with acrylic acid in benzene solvent with addition of p-hydroxyquinoline and p-toluenesulfonic acid and boric acid. 2-Propenoyloxyethoxy)benzoic acid is produced. Next, dimethylacetamide and 2,6-di-t-butyl-p-
The acid chloride compound of formula () is obtained by reacting thionyl chloride in the presence of methylphenol. Further, the azo compound of the general formula () is p-
substituted aniline

[Formula] (R ² is as defined above) and phenol or m-cresol. That is, after treating p-substituted aniline with hydrochloric acid, it was treated with a phenol sodium salt buffer or m in the presence of sodium nitrite.
- An azo compound of the general formula () is obtained by reacting with a cresol sodium salt buffer. The azo bond-containing acrylic ester compound obtained by the present invention is a crystalline solid in normal state, and has liquid crystal properties as described above, and is a substance that is particularly useful as a stationary phase in gas chromatography. . In addition, since this compound has a polymerizable unsaturated bond (acryloyl group) in its molecular formula, it can be easily polymerized using a radical polymerization initiator used for the polymerization of general vinyl compounds. A useful new polymer is obtained. In the formula, R ¹ and R ² are the same as above, and n indicates the degree of polymerization, but this polymer generally has a polystyrene equivalent weight average molecular weight of 1000 to 100, which is determined by the GPC method.
It is obtained as having 100000. This polymer exhibits high separation performance as a stationary phase in gas chromatography. In addition, it has a wide range of liquid crystal properties and has a long life when used repeatedly during heating and cooling, making it extremely effective in practical applications. Next, reference examples, examples, and polymerization agents will be described. Reference example 1 4-hydroxybenzoic acid in 175ml of ethanol
69 g (0.5 mol) was added thereto, and while cooling, 75 g of potassium hydroxide dissolved in 75 ml of water was added. After adding a small amount of potassium iodide, the mixture was refluxed with stirring and 44 g (0.55 mol) of 2-chloroethanol was added using a dropping funnel over 3 hours. After refluxing for 20 hours, ethanol was distilled off and the reaction mixture was diluted with 500 ml of water. After washing with ether, adjust the pH to 4 with hydrochloric acid, filter, and dry to obtain 70 g of white solid, which is 4-(2-hydroxyethoxy)benzoic acid.
(yield 76.9%). It was further recrystallized from ethanol. The melting point of this material was 181°C. 4-(2-hydroxyethoxy)benzoic acid 36.4
g (0.2 mol) and p-hydroquinoline 8 g, p-
8 g of toluenesulfonic acid and 200 mg of boric acid were added to a mixture of 120 ml of benzene and 120 ml of acrylic acid. After refluxing for 15 hours, the mixture was cooled to room temperature, 4 times the amount of ether was added, and extracted with warm water. The ether layer was dehydrated with sulfur salt and then distilled to recover the ether. Next, it is recrystallized from 2-propanol and 4-(2
38 g (yield: 80.5%) of a white solid, which is benzoic acid (-propenoyloxyethoxy), was obtained. The melting point of this material was 141°C. Reference example 2 12.3g (0.1g) of p-methoxyaniline as a raw material
mol) into 40 ml of distilled water, add dilute hydrochloric acid (concentrated hydrochloric acid 30 ml)
(diluted to 100 ml with distilled water) was added dropwise. 5℃
The mixture was cooled to a temperature of 1.5 ml, and 4 g (0.1 mol) of sodium nitrite dissolved in 16 ml of distilled water was added dropwise. After stirring for 1 hour while maintaining the temperature at 5°C, m-cresol sodium salt buffer {m-cresol 10.8 g (0.1 mol)
4 g (0.1 mol) of sodium hydroxide and 12 g of sodium carbonate were dissolved in 170 ml of distilled water}, and the above solution was added dropwise while stirring. After neutralization with hydrochloric acid, the solid content obtained by filtration was redissolved in ether. The ether was distilled off and the residue was dried. It was dissolved in ethanol again and recrystallized by adding hexane to obtain p-(p'-methoxyphenylazo)m-cresol in a yield of 66%. The melting point of this material was 136°C. Reference Example 3 Using 14.9 g (0.1 mol) of p-butylaniline as a raw material, the same procedure as in Reference Example 2 was carried out, and by using hexane as the recrystallization solvent, p-
(p'-Butylphenylazo)m-cresol was obtained in a yield of 78%. The melting point of this material was 66°C. Reference example 4 13.7g (0.1g) of p-ethoxyaniline as a raw material
mol) and operated in the same manner as in Reference Example 2. Recrystallization was performed by dissolving in benzene and adding hexane.
(p'-ethoxyphenylazo)m-cresol was obtained in a yield of 78%. The melting point of this material was 121°C. Reference Example 5 Using 12.1 g (0.1 mol) of p-ethylaniline as a raw material, the same procedure as in Reference Example 2 was carried out, and by using hexane as a recrystallization solvent, p-
(p'-ethylphenylazo)m-cresol was obtained in a yield of 71%. The melting point of this material was 98°C. Reference Example 6 In Reference Example 2, m-cresol sodium salt buffer was replaced with phenol sodium salt buffer {9.4 g (0.1 mol) of phenol, 4 g (0.1 mol) of sodium hydroxide, and 12 g of sodium carbonate were dissolved in 170 ml of distilled water} and benzene as the recrystallization solvent to obtain p-(p'-methoxyphenylazo)phenol in a yield of 70%. The melting point of this material was 146°C. Reference example 7 13.7g of p-ethoxyaniline (0.1
mol) and operated in the same manner as in Reference Example 6, recrystallization was performed by dissolving in ethanol and adding hexane to obtain p-(p'-ethoxyphenylazo)phenol in a yield of 80%. The melting point of this substance is
It was 127℃. Reference example 8 14.9g of p-m-butylaniline as raw material
(0.1 mol), operated in the same manner as in Reference Example 6, and used hexane as the recrystallization solvent.
(p'-n-butylphenylazo)m-cresol was obtained in a yield of 90%. Example 1 7.08 g (0.03 mol) of 4-(2-propenoyloxyethoxy)benzoic acid, 2 drops of dimethylacetamide, 2,6-di-t-butyl-p-methylphenol, and 20 ml of thionyl chloride were stirred for 30 minutes. while heating to 45°C. Thionyl chloride was removed by vacuum distillation, and the remaining acid chloride was dissolved in 50 ml of dehydrated ether. And intermediate raw material p-(p'-
methoxyphenylazo) m-cresol 7.26g
(0.03 mol) of triethylamine dissolved in 5 ml
A solution of 100 ml of and tetrahydrofuran was cooled to 5° C. and added dropwise over 30 minutes. After reacting for 3 hours, the mixture was filtered and the filtrate was removed. The solid residue was dissolved in chloroform, washed with water, and dehydrated with boron sulfate. Thereafter, it was recrystallized with ethanol to obtain 10.19 g of pure solid. When we measured the infrared absorption spectrum of this substance, we found that the absorption due to the ester group was at 1730cm ^-1 and the absorption due to the phenyl group (1610, 1589, 1513,
1425, 1263, 1228 ^{cm -1} etc.), and absorption at 2855 cm ^-1 by methoxy group also appeared. Next, when a mass spectrum was measured using the direct introduction method, a molecular weight peak of 460 was detected. and
When the NMR spectrum was measured, the methyl group bonded to the phenyl group was 2.80 ppm, the methoxy group bonded to the phenyl group was 4.01 ppm, the two methylenes sandwiched between the ether bonds were 4.59 ppm, and the vinyl group of the acrylate ester was 4.59 ppm. 6.12ppm, 6.45ppm,
At 6.68 ppm, phenyl groups appeared in a complex manner at 7 to 9 ppm, and it was found that this was a new substance, acrylic acid ester monomer [M ₁ ]. Furthermore, when this material was observed using a polarizing microscope with a heating stage, when the temperature was increased to 90°C or higher, a fibrous structure characteristic of nematic liquid crystals was observed. Then, if you increase the temperature further
At temperatures above 168°C, no tissue image was observed, indicating that the liquid crystal had a nematic range of 69°.
The transition temperature was also confirmed by DSC and was consistent with the above temperature. Example 2 In Example 1, 8.04 g (0.03
When the same operation was performed using mol), the pure solid content was
8.46g was obtained. When this infrared absorption spectrum was measured, absorption due to ester groups was observed at 1732 cm ^-1 and absorption due to a series of phenyl groups, and absorption due to methylene groups was observed.
2950cm ^-1 and 2880cm ^-1 also appeared strongly. Next, when we measured the mass spectrum using the direct introduction method, a molecular weight peak of 486 appeared. and NMR
When the spectrum was measured, compared to Example 1, the methoxy group bonded to the phenyl group disappeared, and the butyl group bonded to the phenyl group was replaced.
CH ₃ ; 1.00ppm, −CH ₂ CH ₂ −; 1.50ppm,

[Formula] appeared at 2.70 ppm, and it was found that this was a new substance, acrylic acid ester monomer [M ₂ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 45° from 75°C to 120°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Example 3 When the same procedure as in Example 1 was carried out using 7.68 g (0.03 mol) of p-(p'-ethoxyphenylazo)m-cresol as the intermediate raw material, the pure solid content was
12.05g was obtained. When this infrared absorption spectrum was measured, a series of absorptions due to phenyl groups were observed, including an ester group at 1728 cm ^-1 . Next, when a mass spectrum was measured using the direct introduction method, a molecular weight peak of 474 appeared. Then, when the NMR spectrum was measured, compared to Example 1, the methoxy group bonded to the phenyl group disappeared, and instead, the ethoxy group bonded to the phenyl group became CH ₃ ;
1.15ppm,

[Formula] appeared at 4.22 ppm, and it was found that this was a new substance, acrylic acid ester monomer [M ₃ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 68° from 108°C to 176°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Example 4 When the same procedure as in Example 1 was carried out using 7.20 g (0.03 mol) of p-(p'-ethylphenylazo)m-cresol as the intermediate raw material, the pure solid content was 9.76.
I got g. When this infrared absorption spectrum was measured, a series of absorptions due to phenyl groups were observed, including absorption due to ester groups at 1725 cm ^-1 . Then, when the NMR spectrum was measured, compared to Example 1, the methoxy group bonded to the phenyl group disappeared, and instead, the ethyl group bonded to the phenyl group became CH ₃ ;
1.33ppm,

[Formula] appeared at 2.81 ppm, and it was found that this was a new substance, acrylic acid ester monomer [M ₄ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 40° from 81°C to 121°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Example 5 In Example 1, 6.84 g (0.03 mol) of p-(p'-methoxyphenylazo)phenol was used as an intermediate raw material.
When the same operation was performed using
I got it. When this infrared absorption spectrum was measured, a series of absorptions appeared at 1740cm ^-1 due to the ester group, and a series of phenyl groups, and absorption due to the methoxy group also appeared.
It appeared at 2855cm ^-1 . Next, when a mass spectrum was measured using the direct introduction method, a molecular weight peak of 446 appeared. Furthermore, when an NMR spectrum was measured, it was found that, compared to Example 1, the methyl group bonded to the phenyl group disappeared, and the rest remained the same. Therefore, this was found to be an acrylic acid ester monomer [M ₅ ], which is a new substance. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 126° from 114°C to 240°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Example 6 In Example 1, 7.26 g (0.03 mol) of p-(p'-ethoxyphenylazo)phenol was used as an intermediate raw material.
When the same operation was performed using , 7.49 g of pure solid content was obtained. When this infrared absorption spectrum was measured, an absorption due to the ester group appeared at 1740 cm ^-1 , and a series of absorptions due to the phenyl group also appeared. Next, when a mass spectrum was measured using the direct introduction method, a molecular weight peak of 460 was detected. Further NMR
When the spectrum was measured, it was found that, compared to Example 3, the methyl group bonded to the phenyl group disappeared, but the rest was the same. Therefore, this was found to be an acrylic acid ester monomer [M ₆ ], which is a new substance. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 133° from 100°C to 233°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Example 7 When the same procedure as in Example 1 was carried out using 7.56 g (0.03 mol) of p-(p'-n-butylphenylazo)phenol as the intermediate raw material, the pure solid content was 7.38.
I got g. When this infrared absorption spectrum was measured, an absorption due to the ester group appeared at 1740 cm ^-1 , and a series of absorptions due to the phenyl group also appeared. moreover
When the NMR spectrum was measured, it was found that, compared to Example 2, the methoxy group bonded to the phenyl group disappeared, and the rest was the same. Therefore, this was found to be an acrylic acid ester monomer [M ₇ ], which is a new substance. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 79° from 102°C to 181°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 1 2 g of acrylic acid ester monomer [M ₁ ] was dissolved in 20 ml of tetrahydrofuran, and azobisisobutyronitrile was added as a polymerization initiator in an amount of 1 mol percent based on the monomer, and the mixture was reacted at 60° C. for 8 hours under a nitrogen atmosphere. The produced polymer was transferred into ether cooled to 5°C and precipitated. The precipitate was redissolved in chloroform and precipitated in the same solvent, and after filtration,
After drying, a solid content of 0.30 g was obtained. When this NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₁ ].

It turns out that [formula] has become. Then, when dissolved in tetrahydrofuran and determined by GPC method, the weight average molecular weight in terms of polystyrene was found to be 5734.
It was hot. Therefore, this substance is a new polymer [P ₁ ]
It turns out that it is. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 163° from 88°C to 245°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 2 Using 2 g of acrylic acid ester monomer [M ₂ ], the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.10 g. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₂ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method and was 20250.
It was found to be a new polymer [P ₂ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 163° from 80°C to 243°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 3 Using 2 g of acrylic acid ester monomer [M ₃ ], the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.52 g. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₃ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method to be 7827.
It was found to be a new polymer [P ₃ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 160° from 95°C to 255°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 4 Using 2 g of acrylic acid ester monomer [M ₄ ], the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.56 g. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₄ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method and was 8702.
It was found to be a new polymer [P ₄ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 142° from 81°C to 223°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 5 Using 2 g of acrylic acid ester monomer [M ₅ ], the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.84 g. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₅ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method and was 11760.
It turned out to be a new polymer [P ₅ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 175° from 110°C to 285°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 6 Using 2 g of acrylic acid ester monomer [M ₆ ], the same procedure as in Polymerization Example 1 was carried out to obtain 0.44 g of solid content. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₆ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method and was 6019.
It turned out to be a new polymer [P ₆ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 160° from 95°C to 255°C. When the transition temperature was also confirmed by DSC, it matched the above temperature. Polymerization Example 7 Using 2 g of acrylic acid ester monomer [M ₇ ], the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.66 g. When the NMR spectrum was measured, the absorption of CH ₂ =CH- based on acrylic acid disappeared compared to the acrylic acid ester monomer [M ₇ ].

It turns out that [formula] has become. The weight average molecular weight was determined by GPC method and was 13790.
It was found to be a new polymer [P ₇ ]. Furthermore, when this material was observed using a polarizing microscope, it was found to be a nematic liquid crystal with a temperature range of 173° from 102°C to 275°C. When the transition temperature was also confirmed by DSC, it matched the above temperature.

Claims (1)

[Claims] 1. General formula (R ¹ in the formula is a hydrogen atom or methyl group, R ² is C _n
An azo bond-containing acrylic ester compound represented by a group represented by H _2n+1 or OC _n H _2n+1 , where m is an integer of 1 to 4.