JP2691300B2 - Organic boron-containing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to 2- (p-substituted phenyl) -1, which has a rod-like side chain,
Regarding the organic boron-containing polymer having a 3,2-dioxaborinane skeleton, this polymer is expected to be applied to the field of optoelectronics, especially optical recording materials, polarizing plates, and nonlinear optical materials.

[Conventional technology]

The organic boron-containing polymer of the present invention is a compound not described in the literature.

[Problems to be Solved by the Invention] An object of the present invention is to provide a novel organic boron-containing polymer.

[Means for solving the problem]

The present invention has the general formula [I] (In the formula, R is a linear alkyl group having 1 to 13 carbon atoms, and 1 carbon atom.
To 13 linear alkoxy groups, 2 to 14 linear alkoxycarbonyl groups, a halogen atom or a cyano group, X is a hydrogen atom or a methyl group, and n is an integer of 2 to 15). It is an organic boron-containing polymer having a repeating unit.

The weight average molecular weight of the polymer having the repeating unit of the general formula [I] is about 3,000 to 1,000,000, preferably 5,000 to
It is 1,000,000. When applied to the field of optoelectronics, it cannot be specified because it varies depending on the type of R group and the value of n in the above general formula [I], but a particularly preferable range of the weight average molecular weight is 5,000 to 400,000. If the molecular weight is less than 3,000, the physical properties are not constant and it is not practically preferable.

The organoboron-containing polymer of the present invention has the following general formula [I
I] It is obtained by polymerizing an organoboron-containing monomer represented by the formula (wherein R, X and n have the same meanings as described above), and these monomers can be produced, for example, as follows.

(Where n, R and X have the same meanings as above, DBU is 1,8-
Diazabicyclo [5,4,0] undec-7-ene).

The organoboron-containing polymer of the present invention can be obtained by polymerizing one or two or more types of monomers thus obtained.

As the polymerization method, for example, various methods such as thermal radical polymerization, radical polymerization using an initiator, radical polymerization using ultraviolet rays or radiation, and anionic polymerization using butyl lithium as an initiator can be adopted.

Various kinds of initiators such as peroxides and diazo compounds are known as initiators for radical polymerization. Benzoyl peroxide,
A relatively easy-to-handle compound such as azobisisobutyronitrile is used.

There are various polymerization methods such as bulk polymerization, slurry polymerization and solution polymerization, and any of them may be used.

The polymerization time varies depending on the polymerization temperature and the kind of the initiator, but when benzoyl peroxide or azobisisobutyronitrile is used, for example, a polymerization temperature of 30 to 90 ° C for 1 to 20 hours is suitable.

The polymer molecular weight can be adjusted by a known method, for example, by adding a molecular weight modifier or adjusting the concentration of the polymerization initiator with respect to the monomer.

A known inert solvent is used as the solvent in the case of performing the solution polymerization method, and for example, solvents such as dichloromethane, tetrahydrofuran, benzene, toluene and xylene are suitable.

The organoboron-containing polymer of the present invention obtained by polymerizing in this way is considered to be used in the field of optoelectronics, for example, but depending on the needs of each application, it may be copolymerized with another polymerizable monomer containing no boron. , Mixing different kinds of organic boron-containing polymers of the present invention, mixing with other polymers,
The organoboron-containing polymer of the present invention can be improved and applied by adding stabilizers, plasticizers and the like.

[Functions and Effects of the Invention]

The organoboron-containing polymer of the present invention is a novel compound, and is expected to be applied to the field of optoelectronics, particularly optical recording materials, polarizing plates, nonlinear optical materials and the like.

〔Example〕

Hereinafter, the present invention will be described by way of examples. In the examples,% represents% by weight.

Production Example 1 Synthesis of 2-bromoalkyl-1,3-propanediol [B] A 200 cc three-necked flask equipped with a stirrer, a dropping funnel and a reflux condenser was charged with 76 mmol of dibromoalkane and 50 ml of absolute ethanol, and was placed in a nitrogen stream. Then, a solution prepared by previously mixing and dissolving 76 mmol of diethyl malonate and 76 mmol of sodium ethoxide in 50 ml of absolute ethanol was added dropwise while heating to reflux ethanol. The drip was finished in 15 minutes,
The mixture was stirred and reacted under reflux of ethanol for 17 hours. After completion of the reaction, ethanol was distilled off and the residue was extracted with ether.
The ether solution was washed with a 10% aqueous sodium hydroxide solution and water in this order, and dried over anhydrous sodium sulfate. Unreacted diethyl malonate and dibromoalkane were distilled off from the ether solution under reduced pressure to obtain a compound of the following formula [A].

Br (CH ₂ ) _n CH (CO ₂ C ₂ H ₅ ) ₂ [A] Example. The proton NMR peak when n = 8 is This compound was used in the next reaction without further purification.

In a two-necked four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 40 mmol of the above compound [A] and 500 m of methanol were added.
After l was charged and dissolved, 594 mmol of sodium borohydride was gradually added over 30 minutes while stirring. Immediately after the start of feeding, heat generation starts and ethanol begins to reflux, but the feeding should be done so that the reflux continues gently. Heat to a gentle reflux even after the addition is complete, and
Allowed to react for minutes. After the reaction, insoluble materials were removed with a glass filter and the methanol solution was concentrated. The concentrate was extracted with ether, and the ether solution was concentrated and then purified by column chromatography (200 mesh silica gel 100 g, eluent: benzene to ethyl acetate gradient) to give 2-bromoalkyl-1,3-propanediol. [B] was obtained.

Table 1 shows the results together with the properties and physical properties of each compound obtained.

Production Example 2 Synthesis of 2- (4'-substituted phenyl) -4-bromoalkyl-1,3,2-dioxaborinane [C] A stirrer, a thermometer and an azeotropic dehydrator with a reflux condenser were provided.
A 200 cc three-necked flask was charged with 10 mmol of 2-bromoalkyl-1,3-propanediol obtained in Production Example 1, 10 mmol of 4-substituted phenylboronic acid and 50 ml of toluene, and the azeotropic dehydration reaction was carried out at the reflux temperature. The reaction was completed in about 1 to 2 hours, toluene was distilled off under reduced pressure, and the residue was isolated and purified by column chromatography (200 mesh silica gel 60 g, developing solvent: dichloroethane) to give 2- (4'-substituted phenyl)-.
4-Bromoalkyl-1,3,2-dioxaborinane [C]
I got

Table 2 shows the results together with the properties and physical properties of each compound obtained.

(Note) The symbols in Table 2 indicate the following.

C: Crystal phase, S _A : Smectic A phase of liquid crystal phase, I: Isotropic liquid phase.

Production Example 3 2- (4′-substituted phenyl) -4-acryloxyalkyl-1,3,2-dioxaborinane [II] (X
= H) 2- (4'-substituted phenyl) -4-bromoalkyl-1,3,2-obtained in Preparation Example 2 was placed in a 50 cc three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Anhydrous benzene solution of 2 mmol of dioxaborinane [C] and 3 mmol of acrylic acid 10
5 ml of anhydrous benzene solution containing 3 mmol of 1,8-diazadicyclo [5,4,0] undec-7-ene (DBU) was charged under a nitrogen stream and dissolved with stirring. After stirring at a reaction temperature of 60 ° C for 2 hours, returning to room temperature after completion of the reaction, distilling off benzene, isolation and purification by column chromatography (200 mesh silica gel 20 g, developing solvent: dichloromethane) and recrystallization from hexane, 2- (4'-substituted phenyl) -4-acryloxyalkyl-1,3,2-dioxaborinane [II] was obtained.

Production Example 4 2- (4'-Substituted Phenyl) -4-methacryloxyalkyl-1,3,2-dioxaborinane [II]
Except using methacrylic acid in place of the synthetic acrylic acid (X = CH ₃₎ was synthesized under the same conditions as in Production Example 3, 2- (4'-substituted phenyl) -4-methacryloxy alkyl -1 1,3,2-Dioxaborinane [II] was obtained.

The results are shown in Table 3 together with the properties and physical properties of each compound obtained in Production Examples 3 and 4.

Example 1 Synthesis of Organic Boron-Containing Polymer (Homopolymer) A predetermined amount of each compound [II] obtained in Production Examples 3 and 4, azobisisobutyronitrile and dry toluene was put in a 10 ml glass ampoule and frozen. After deaeration, the mouth of the ampoule was sealed and the reaction was carried out under the polymerization conditions shown in Table 4. After the reaction, the mouth of the ampoule was cut off, the mixture was poured into 100 ml of methanol, the precipitated insoluble matter was centrifuged, the fixed matter was dissolved in benzene, freeze-dried and purified to obtain an organic boron-containing polymer.

The polymerization conditions and the polymer yield are shown in Table 4, and the analysis results and properties of the polymer are shown in Table 5.

Example 2 Organoboron-containing polymer (mutual copolymer)
Synthesis of Monomer Obtained in Preparation Example 3 in 10 ml Glass Ampoule
0.35 g of No.5, 0.35 g of monomer No.7, 5.3 mg of azobisisobutyronitrile and 8 ml of dry toluene were put, and after freezing and deaeration, the mouth of the ampoule was sealed and the reaction was carried out at 60 ° C for 10 hours. . The ampoule was cut off, poured into 100 ml of methanol, the precipitated insoluble matter was centrifuged, dissolved in benzene, and freeze-dried for purification to obtain an organic boron-containing polymer. As a result of nitrogen (N) analysis of this polymer, 0.59%
It contained nitrogen. As a result of calculation, it was found that the monomer No. 5 and the monomer No. 7 were copolymerized at a molar ratio of 83.3 to 16.7.

 The analysis results and properties of the obtained polymer are shown below.

IR spectrum NMR spectrum Weight average molecular weight ▲ ▼ = 250,000 (polystyrene standard) Thermal analysis (Note: G, S _A and I have the same meaning as the symbols in Table 5).

[Brief description of the drawings]

1 is the infrared absorption spectrum of polymer No. 1 obtained in Example 1, and FIG. 2 is the proton NMR of the same polymer.
It is a spectrum.

Claims (1)

(57) [Claims] 1. A compound of the formula [I] (In the formula, R is a linear alkyl group having 1 to 13 carbon atoms, and 1 carbon atom.
To 13 linear alkoxy groups, 2 to 14 linear alkoxycarbonyl groups, a halogen atom or a cyano group, X is a hydrogen atom or a methyl group, and n is an integer of 2 to 15). An organic boron-containing polymer having a repeating unit.