JPH083260A - Polyurethane having fluorene skeleton - Google Patents

Abstract

PURPOSE:To prepare a polyurethane which has heat resistance and a film- forming property and is rigid and chemically stable by reacting 9,9-bis [4-(2- hydroxyethoxy)pheny] fluorene (BHPF) with a diisocyanate compd. CONSTITUTION:The amts. of BHPF represented by formula I and the diisocyanate compd. represented by formula II used are, in general, pref. approximately equimolar with each other. For example, benzene or the like may be used as a solvent. When the reaction is carried out at 60 to 150 deg.C, it is completed within about 1 to 10hr. It is also possible to carry out this reaction by a method wherein the diisocyanate is reacted in an excessive amount to synthesize a prepolymer having an isocyanate group at its both ends and a diamine or the like is added to extend the chain and to carry out an intermolecular crosslinking reaction. After the completion of the reaction, the resultant polyurethane having a fluorene skeleton, after the removal of the solvent, is washed with a lower aliph. alcohol and filtered. It has repeating units represented by formula III and a no. average molecular weight of 3000 to 200000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polyurethanes.

[0002]

2. Description of the Related Art Polyurethane is widely used as a transparent conductive film, an organic semiconductor, an organic superconductor, a light and heat sensitive material in the electric and electronic industries, and also in the fields of paints, fibers, synthetic leather and the like. Further, more specifically, it is widely used, for example, in tires, belts, packings, gears, shoe soles and the like. Polyurethanes are obtained by reacting polyester glycols or polyether glycols with diisocyanates. As a typical polyester glycol, a product having a molecular weight of about 1500 to 3000 obtained from ethylene glycol or the like and adipic acid or the like is used, and as the diisocyanate, tolylene diisocyanate or the like is used.

The reaction of polyester glycol or polyether glycol with diisocyanate is carried out by excessively reacting diisocyanate to synthesize a high molecular weight prepolymer having isocyanate groups at both ends, and further diamine, amino alcohol, Glycol is added to extend the chain length and intermolecular crosslinking reaction is performed. Polyurethane has different physical properties depending on the type of these raw materials and the crosslinking conditions,
Generally, it has excellent oil resistance and abrasion resistance, but also has a disadvantage of low heat resistance, and there is little known one having film forming ability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyurethane having a fluorene skeleton which is rigid and chemically stable, which has heat resistance and film forming ability.

The polyurethane of the present invention has the general formula (1)

[0006]

Embedded image

It has a repeating unit represented by and has a number average molecular weight of 3,000 to 200,000, preferably 5,000.
Polyurethane in the range of up to 50,000. If the number average molecular weight is too high, the film forming ability tends to decrease.

Polyurethanes having a repeating unit represented by the above general formula (1) are represented by, for example, the formula (2)

[0009]

Embedded image

9.9-bis (4- (2-hydroxyethoxy) phenyl) -fluorene represented by
HPF ”) and the general formula (3)

[0011]

[Chemical 4]

It is produced by reacting diisocyanates represented by:

Examples of the diisocyanates of the general formula (3) include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate (hereinafter referred to as "HDI"). ), Heptamethylene diisocyanate, octamethylene diisocyanate,
Examples include toluylene diisocyanate (hereinafter referred to as "TDI"), xylylene diisocyanate (hereinafter referred to as "XDI") and the like.

The ratio of BHPF and diisocyanates used is usually about equimolar. The reaction is
It is usually carried out in a suitable solvent. Here, the solvent is not particularly limited, but it is preferable to use, for example, benzene, toluene, chlorobenzene, o-dichlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. The reaction is usually 60 to 1
It is completed in about 1 to 10 hours under a temperature condition of about 50 ° C.

After completion of the reaction, the resulting polyurethane represented by the general formula (1) of the present invention, after removing the solvent,
It is isolated and purified by a conventional means such as a method of washing and filtering with a lower aliphatic alcohol such as methanol.

Regarding the reaction between BHPF and diisocyanates, diisocyanate is excessively reacted to synthesize a prepolymer having isocyanate groups at both ends, and further diamine, aminoalcohol, glycol or the like is added. In addition, the chain length can be extended and an intermolecular crosslinking reaction can be performed.

[0017]

The novel polyurethane having a fluorene skeleton of the present invention has heat resistance and film forming ability, and is rigid and chemically stable.

[0018]

Example 1 In a 300 ml container equipped with a stirrer, a nitrogen blowing tube, a cooling tube, and a thermometer, 4.38 g (10 mmo)
1) BHPF and 100 ml of chlorobenzene were put, and 50 ml of nitrogen was blown per minute to purge the inside of the container with nitrogen. Next, after adding 1.68 g (10 mmol) of HDI, the mixture was vigorously stirred at 100 ° C. for 3 hours while blowing nitrogen. After completion of the reaction, chlorobenzene was removed by distillation under reduced pressure, the solid was washed with 30 ml of methanol, and then taken out by filtration. The obtained solid is
Further purification was carried out by washing and filtering twice with 30 ml of diethyl ether. 3.1 g of white solid was obtained.

Film formation test 0.1 g of the obtained white solid was dissolved in 10 ml of warm acetone and poured evenly on a glass board, and the solvent was removed to obtain a transparent film. The IR analysis result of the obtained film is shown below.

IR (film, cm ^-1 ) 3300 (-N
_{H -), 2950,1450,770 (-CH 2} -),
1730 (C = O), 1600,820 (-C 6 H
₄ -), 1520,1240 (-CONH-)

[0021]

Example 2 In a 300 ml container equipped with a stirrer, nitrogen blowing tube, cooling tube, and thermometer, 4.38 g (10 mmo)
BHPF of 1) and 100 ml of dimethylformamide were added, and 50 ml of nitrogen was blown in every minute to replace the inside of the container with nitrogen. Then 1.68 g (10 mmol) of TDI
After adding, the mixture was vigorously stirred at 100 ° C. for 3 hours while blowing nitrogen. After completion of the reaction, chlorobenzene was removed by distillation under reduced pressure, the solid was washed with 30 ml of methanol, and then taken out by filtration. The obtained solid was purified by further washing and filtering twice with 30 ml of diethyl ether. 2.8 g of white solid was obtained.

Film formation test 0.1 g of the obtained white solid was dissolved in 10 ml of warm acetone, and the solution was evenly poured on a glass board, and then the solvent was removed to obtain a transparent film.

[0023]

Example 3 In a 300 ml container equipped with a stirrer, nitrogen blowing tube, cooling tube, and thermometer, 4.38 g (10 mmo)
BHPF of 1) and 100 ml of dimethylformamide were added, and 50 ml of nitrogen was blown in every minute to replace the inside of the container with nitrogen. Then 1.68 g (10 mmol) of XDI
After adding, the mixture was vigorously stirred at 100 ° C. for 3 hours while blowing nitrogen. After completion of the reaction, chlorobenzene was removed by distillation under reduced pressure, the solid was washed with 30 ml of methanol, and then taken out by filtration. The obtained solid was purified by further washing and filtering twice with 30 ml of diethyl ether. 2.9 g of white solid was obtained.

Film formation test 0.1 g of the obtained white solid was dissolved in 10 ml of warm acetone and poured evenly on a glass board, and the solvent was removed to obtain a transparent film.

[Molecular Weight Measurement Result] The number average molecular weight of the white solid (polyurethane) obtained in each Example was measured by gel permeation chromatography. Example 1 is 11000, Example 2 is 9600, and Example 3 is 14
It was 000.

[Viscosity Measurement Result] The viscosity η (30 ° C., dimethylformamide) of the white solid (polyurethane) obtained in each example was measured with a Ubbelohde viscometer. Example 1 had 0.142 sp, Example 2 had 0.085 sp, and Example 3 had 0.120 sp.

[Brief description of drawings]

FIG. 1 is an IR chart of the white solid (polyurethane) obtained in Example 1.

FIG. 2 ¹ H-NMR chart of white solid (polyurethane) obtained in Example 1.

Claims (1)

[Claims] 1. A compound represented by the general formula (1): And has a number average molecular weight of 30
Polyurethane in the range of 00 to 200,000.