JPH02155924A - Fluorescent polymer and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the title polymer with excellent heat resistance useful as a starting material for a display material, a decorative material, etc., by reacting a fluoresceine (or its deriv.) with a specified compd. CONSTITUTION:The title polymer having repeating units of formula V (wherein Y is H or an alkali metal atom) and a reduced viscosity (at 30 deg.C) in a soln. of a concn. of 0.2g/dl in N-methylpyrrolidone of 0.1dl/g or larger is obtd. by reacting a fluoresceine (or its deriv.) of formula I (wherein R<1> is a 1-6C alkyl or a 6-8C aryl; m is 0-3) with a compd. of the formula X-Ar-X (wherein Ar is a group of formulas II-IV; X is a halogen) in the presence of an alkali metal compd. (e.g. K2CO3) and pref. in a neutral polar solvent (e.g. N- methylpyrrolidone).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel fluorescent polymer and a method for producing the same. More specifically, the present invention relates to a novel fluorescent polymer and a method for producing the same. This invention relates to a fluorescent polymer useful for materials, toys, etc., and a method for efficiently producing this polymer through simple steps.

[Prior Art and Section 1 to be Solved by the Invention Fluorescent polymers are useful as materials for forming nighttime signs, ornaments, etc., and are actually widely used in these applications.

Examples of the fluorescent polymer include thermoplastic resins such as polymethyl methacrylate, polystyrene, and vinyl chloride resins, and fluorescein.

Conventionally, materials prepared by kneading organic phosphors such as rhodamine B and eosin Y have been commonly used.

However, conventional fluorescent polymers have problems in that the organic phosphor component is more likely to separate from the polymer and that they do not have sufficient heat resistance.

Therefore, as a solution to this problem,
No. 62589 discloses a fluorescent polymer obtained by introducing a fluorescein residue into the side chain of a polymer having a vinyl main chain via an amide bond.

However, the manufacturing process for fluorescent polymers having such a structure is complicated, and the heat resistance is still not sufficient.

The present invention has been made based on the above circumstances.

An object of the present invention is to provide a fluorescent polymer having sufficient heat resistance and a method for efficiently producing this fluorescent polymer using simple steps.

[Means for Solving the Problems] In order to solve the problems described above, the present inventor has conducted extensive research and found that a fluorescent polymer having a specific repeating unit exhibits excellent heat resistance. The present invention was achieved by discovering that a specific fluorescent polymer can be efficiently produced in a simple process by a specific reaction using a specific compound.

That is, the structure of the invention of claim 1 has a repeating unit represented by the linear formula % formula %], and is reduced at a temperature of 30°C in a droplet with a concentration of 0.2 g/d4Q using N-methylpyrrolidone as a solvent. It is a fluorescent polymer characterized by having a viscosity of 0.1 dJL/g or more, and the structure of the invention according to claim 2 is one of the following formulas (■): where R' has 1 to 1 carbon atoms. 6 alkyl group or aryl group having 6 to 8 carbon atoms, and Y is either a hydrogen atom or an alkali metal atom. In addition, 1m is any integer of 0 or 1 to 3 [wherein, in formula (U), R1 is an alkyl group of carbon atoms a1 to 6 or an aryl group of carbon atoms of 6 to 8, m is 0 or an integer of 1 to 3 is one of the integers. ] A compound represented by the following formula (m); ] The method for producing a fluorescent polymer according to claim 1, wherein the fluorescent polymer is reacted with a compound represented by the following formula in the presence of an alkali metal compound.

One of the important points about the fluorescent polymer according to claim 1 is that it has a repeating unit represented by the formula (I), and that it has a repeating unit of 0.2 g/
The reduced viscosity at a temperature of 30°C in a solution with a concentration of d is 0.1
dfL/g or more.

If the reduced viscosity is less than 0.1 dll/g, the mechanical strength when used as a molding material will be insufficient.

The fluorescent polymer according to claim 1 is prepared according to the method according to claim 2, and a compound represented by the formula (n);
It can be produced by reacting the compound represented by the formula (III) in the presence of an alkali metal compound.

In the method of the present invention, specific examples of the compound represented by the formula (■) used include fluorescin represented by , difluorodiphenylsulfone represented by , difluorobenzonitrile represented by N , difluorobenzonitrile represented by N ( However, in these formulas, m has the same meaning as above.

) Examples include fluorescin derivatives such as.

Among these, fluorescin is preferred.

Specific examples of the compound represented by the formula (m) that can be used include dichlorodiphenyl sulfone represented by the following, and dichlorobenzonitrile represented by the following.

Examples include difluorobenzophenone represented by , and dichlorobenzophenone represented by .

Among these, preferred are dichlorodiphenyl sulfone, difluorobenzonitrile, and difluorobenzophenone.

In the method of the present invention, together with the compound represented by the formula (II) and the compound represented by the formula (m),
A copolymer component can be used if necessary.

As the copolymerization component, the following formula (■): (However, (■
), where Z is a direct bond, an oxygen atom, a sulfurized atom, a sulfonyl group, an alkyl group or a cycloalkyl group, or a phenyl group. ].

and +CU, dimension'r= [q is an integer from 1 to 10. ]
, R2 is an alkyl group having 1 to 4 carbon atoms,
Either a phenyl group or a cyclohexyl group.

), Or the following formula (V); Examples include compounds represented by:

Among these, preferred is the compound represented by the above formula (IV), and particularly preferred is 2,2-bis(4
-hydroxyphenyl)propane.

In the method of the present invention, the compound represented by the formula (II), the compound represented by the formula (m), and the copolymerization component used as necessary are combined in the presence of an alkali metal compound. , usually reacted in a neutral polar solvent to obtain the fluorescent polymer according to claim 1.

The alkali metal compound to be used is not particularly limited as long as it can convert the compound represented by formula (II) into an alkali metal salt.
Preferred are alkali metal carbonates, alkali metal hydrocarbons, and alkali metal hydroxides.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

Among these, preferred are sodium hydroxide and potassium hydroxide.

In the method of the present invention, by using the alkali metal compound, it is possible to obtain a fluorescent polymer in which Y in the formula (1) is the alkali metal atom. After treating with an acid to obtain a fluorescent polymer in which Y in formula (1) is a hydrogen atom, if the desired alkali metal compound is further reacted with the fluorescent polymer, the desired alkali can be formed. Metals can be introduced. Preferred Y atoms in formula CI) include lithium, sodium, potassium, cesium, and rubidium atoms, and particularly preferred are sodium and potassium atoms.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,
N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N-isopropyl-2-
Pyrrolidone, N-isobutyl-2-pyrrolidone, N-n
-Propyl-2-pyrrolidone, N-n-tuty-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N- Methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2
-piperitone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, l-methyl-1-oxosulfolane, l-ethyl-1-oxosulfolane,
Examples include 1-phenyl-1-oxosulfolane, dimethylimitazolidinone, and diphenylsulfone.

In the method of the present invention, the proportion of the compound represented by the formula (n) and the compound represented by the formula (m) is determined based on the ratio of the compound represented by the formula (II) to the compound represented by the formula (II).
The molar ratio of the compound represented by m), usually 0.98 to
l, 02, preferably 1.00 to 1.01
This is the percentage of

In addition, when using the above copolymer component, the above formula (II
) The proportion of the polymer obtained by the polymerization reaction between the compound represented by formula (m) and the compound represented by formula (m) is preferably 5 mol % or more. In this case, the polymer is 5
If the amount is less than mol %, the fluorescence intensity of the resulting fluorescent copolymer may become low.

The proportion of the alkali metal compound to be used varies depending on the type of the alkali metal compound and cannot be uniformly defined.For example, when the alkali metal carbonate is used, the proportion of the alkali metal carbonate to be used is formula(
The molar ratio of the alkali metal carbonate to the compound represented by II) is usually 3.0 or more, preferably 3.05 or more.

Is there any particular restriction on the amount of the Moeki neutral polar solvent used?Usually, the amount of the compound represented by the above formula (IN, the compound represented by the above formula (m), and the alkali metal compound) is 100% by weight. The amount is selected from 200 to 1000 parts by weight.

In order to obtain the fluorescent polymer according to claim 1 by the production method according to claim 2, for example, a compound represented by the formula (■) and the formula (m) are added to the neutral polar solvent. The compound represented by the formula and the alkali metal compound are added at the same time or in appropriate portions, usually at a concentration of 120
If the reaction temperature is less than 120°C, the reaction rate is too slow to be practical;
Exceeding this may lead to side reactions.

Moreover, the reaction time in this reaction is usually 0.5 hours to 10 hours, preferably 1 hour to 5 hours.

The fluorescent polymer according to claim 1 obtained in this way is a high molecular weight polymer having a repeating unit represented by the formula (I), and its reduced viscosity is determined by using N-methylpyrrolidone as a solvent. In a solution with a concentration of 0.2 g/dl,
Measured at a temperature of 30°C (a or 0.1dJ1/
g or more.

The fluorescent polymer of the present invention has a high glass transition temperature and a high thermal decomposition initiation temperature, and has sufficient heat resistance, and can be suitably used for, for example, display materials, book packaging materials, toy forming materials, and the like.

The fluorescent polymer having the above-mentioned excellent properties can be produced by a simple process according to the method of claim 2.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) Internal volume 3 equipped with a stirring device, an argon gas blowing tube, a thermocouple and a Dean-Starck trap filled with toluene.
In a 00s+41 separable flask, 26.746 g (0.08 mol) of fluorescin and 23.202 g (0.08 mol) of 4.4' dichlorodiphenyl sulfone were added.
Add 0.144 mol of potassium dicarbonate and 100 s of N-methylpyrrolidone, and heat at 215° in an oil bath.
The mixture was heated at C for 90 minutes. During this time, water produced by adding toluene and refluxing was distilled off. Next, toluene was removed and reaction was carried out at a temperature of 205° C. for 4 hours.

After the reaction is complete, the product is poured into 2 liters of water containing oxalic acid to precipitate the polymer, and the resulting polymer is placed in a blender.
(manufactured by Warning Co., Ltd.), washed twice with 1M methanol, washed twice with 1J1 water, and dried to obtain 1 polymer 42. :Ig (
A yield of 96% was obtained.

When we measured the properties of this polymer, we found that the reduced viscosity (
Value measured at a temperature of 60°C for a solution containing N-methylpyrrolidone as a solvent and having a concentration of 0.2 g/d.

The same applies hereafter) 0.41 dl/g, glass transition temperature (Tg) 251 'C1 thermal decomposition initiation temperature (Td)
The temperature was 438°C (5% weight loss in air).

In addition, when IR measurement was performed, it was 1720 cm-'
Absorption due to carboxyl group at position , also.

Absorption due to ether bond was confirmed at the position of 1260C-1.1240cm-'.

The infrared absorption spectrum of this polymer is shown in FIG.

From this result, it is recognized that the obtained polymer has a repeating unit with the following structure.

Furthermore, as a result of measuring the fluorescence spectrum of this polymer,
The excitation maximum wavelength is 4QQnm, and the fluorescence maximum wavelength is 47
It was 0t++s (blue to green).

(Example 2) 0.0 ml of sodium hydroxide was added to a solution in which 1 g of the polymer obtained in Example 1 was dissolved in 50 ml of N-methylpyrrolidone.
A 3 g aqueous solution (1 mJ1) was added to obtain a polymer consisting of repeating units having the following structure.

As a result of measuring the fluorescence spectrum of this polymer, the maximum excitation wavelength was: 190 nm, 470 ns, and the maximum fluorescence wavelength was 570 n- (orange color).

(Example 3) To a solution in which 1 gft of the polymer obtained in Example 1 was dissolved in 50 mJL of N-methylpyrrolidone, 0% potassium hydroxide was added.
．． A 3 g aqueous solution (1 mJl) was added to obtain a polymer consisting of repeating units having the following structure.

The results of measuring the fluorescence spectrum of this polymer.

The excitation maximum wavelength was: 1'l (lnm), 47Qnm, and the fluorescence maximum wavelength was 570n haze (orange color).

(Example 4) In Example 1, 11.239 g (O
, Oa mol) and the reaction time at 205°C was changed from 4 hours to 1 hour. Obtained.

When the properties of this polymer were measured, the reduced viscosity was 0.
．． 41 dfL/g, glass transition temperature (T g) 287
℃, and the thermal decomposition onset temperature (Td) was 441'C (in air, 5% jll! volume reduction).

In addition, when IR measurement was performed, it was 2250cm-'
Absorption by nitrile group at position 1710cm-'
Absorption due to carboxyl group at position 1240
Absorption due to an ether bond was confirmed at the cm-' position.

The infrared absorption spectrum of this polymer is shown in FIG.

From this result, it is recognized that the obtained polymer has a repeating unit with the following structure.

Furthermore, as a result of measuring the fluorescence spectrum of this polymer,
The excitation maximum wavelength is 390 nm, and the fluorescence maximum wavelength is 46 nm.
5 nm (blue).

(Example 5) In Example 1, 4,4'-difluorobenzophenone 17.: 173 g was substituted for 4.4''-dichlorodiphenylsulfone 2: 1.202 g (0.08 mol).
Polymer: 19.
5 g (yield 96%) was obtained.

When the properties of this polymer were measured, the reduced viscosity was 0.
．． 42 dfL/g, glass transition temperature (T g) 245
℃, and the thermal decomposition onset temperature (Td) was 440'C (5% weight loss in air).

Also, when I performed IR measurement, it was found that 1720c■-1
There is also absorption by the carboxyl group at the position.

Absorption due to ether bonds was confirmed at the positions of 1000 cm-' and 1220 cm-', respectively.

The infrared absorption spectrum of this polymer is shown in FIG.

From this result, it is recognized that the obtained polymer has a repeating unit with the following structure.

As a result, the maximum excitation wavelength was 190 nm, and the maximum fluorescence wavelength was 465 nm (blue).

(Example 6) In Example 1, the amount of fluorescin used was 26
．． 746g (0.08 mol) to 13.373g (
0.04 mol) and 2 as a comonomer.
゜2-bis(4-hydroxyphenyl)propane 9.1
Example 1 above, except that 2 g (0.04 mol) was used.
In the same manner as above, a copolymer 37.9 with the following structure was obtained.
g (yield 95%) was obtained.

17.328g <0.076 mol) was used.
In the same manner as in Example 1, 34.6 g (yield: 96%) of a copolymer with the following structure was obtained. The properties of the polymer were measured, and the reduced viscosity was 0.38 db/m.
g, glass transition temperature (T g) 225°C, 8 decomposition onset temperature (Td) 440°C (in air, 5% weight M).

Further, both the infrared absorption spectrum and the fluorescence spectrum were similar to those of Example 1.

(Example 7) In Example 1, the amount of fluorescin used was 26
．． 746 g (0.08 mol) to 1.331 g (
0,004 mol) and 2゜2-bis(4-hydroxyphenyl)propane as a comonomer.When the properties of this polymer were measured, the reduced viscosity was 0.6.
3 d/g, glass transition temperature (T g) 195°C,
8 Decomposition start temperature (Td) 4611°C (in air, 5
% weight loss).

Further, both the infrared absorption spectrum and the fluorescence spectrum were similar to those of Example 1.

[Effects of the Invention] (1) According to the invention as claimed in claim 1, it exhibits a high glass transition temperature and a high thermal decomposition start temperature, has sufficient heat resistance, and has fluorescence, so it can be used, for example, as a display material or a decorative material. The present invention can provide novel fluorescent polymers useful as materials for forming toys, etc.

(2) Furthermore, according to the second aspect of the invention, it is possible to provide a method for producing a fluorescent polymer that can efficiently obtain a polymer that satisfies such unique properties through a simple process.

[Brief explanation of the drawing]

1 to 3 are infrared absorption spectra of examples of the fluorescent polymer of the present invention, respectively.

Claims (2)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in formula (I), Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , R^1 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and Y is either a hydrogen atom or an alkali metal atom. Moreover, m is either 0 or an integer from 1 to 3. ] Fluorescence characterized by having a repeating unit represented by and having a reduced viscosity of 0.1 dl/g or more at a temperature of 30°C in a solution with a concentration of 0.2 g/dl using N-methylpyrrolidone as a solvent. Polymer. (2) Following formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in formula (II), R^1 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms. m is either 0 or an integer from 1 to 3. ] and the following formula (III): There is ▼, and X is a halogen atom. The method for producing a fluorescent polymer according to claim 1, characterized in that the compound represented by the following formula is reacted in the presence of an alkali metal compound.