JPH02223582A - Naphthalenetetracarboxylic acid diimide compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is p-phenylene, -(CH2)m- (m is 11-20) or formula II (n is 1-4); phenylene group is linked to N atom forming the imide ring in formula I; R is H or 1-8C alkyl, provided that R is 2-8C alkyl when X is p-phenylene]. EXAMPLE:N,N'-Bis(4-ethylcarboxyphenyl)-naphthalene-1,4,5,8-tetracarbox ydiimide expressed by formula III. USE:Useful as a polyester material excellent in ultraviolet ray shielding properties. PREPARATION:Naphthalene-1,4,5,8-tetracarboxylic acids and aminocarboxylic acids expressed by formula IV (e.g. ethyl p-aminobenzoate) are subjected to imidation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to naphthalenetetracarboxylic acid diimide compounds. Specifically, the present invention relates to a novel compound useful as a polyester material with excellent ultraviolet blocking properties.

<Prior art> Polyester, represented by polyethylene terephthalate, has been widely used in fibers, films, etc. due to its excellent mechanical and chemical properties, but in recent years, its excellent transparency, gas barrier properties, and safety Due to its hygienic properties, it is attracting attention for its suitability as containers for carbonated drinks, fruit juice drinks, liquid seasonings, edible oils, alcoholic beverages, and wine. In addition, as a new use for polyester film, from the perspective of energy saving and earthquake countermeasures, window lining films for the purpose of blocking heat rays and preventing glass from scattering have shown rapid growth in recent years, and in agriculture and horticulture, agricultural products There is a strong demand for a transparent film that selectively blocks ultraviolet rays in a specific wavelength range for the purpose of promoting growth and increasing yield (for example, Japanese Patent Application Laid-Open No. S3-QG Kogu).

However, although the polyester containers and films of Totara et al. are extremely good at blocking ultraviolet rays at short wavelengths up to about 320 nm, they do not block ultraviolet rays at longer wavelengths.
Visible light and the like are mostly allowed to pass through. For example, if a polyester container is filled with liquid seasonings such as edible oil, mirin, or dressing, and stored for several months, the contents of each filled food may change depending on the storage conditions. Although it has special characteristics, it often causes gradual deterioration of the contents, such as subtle changes in color, taste, and aroma9. Deterioration of the contents is caused by external factors such as oxygen, heat, light, ultraviolet rays, and microorganisms, but in the case of polyester containers, they have relatively excellent oxygen blocking properties, so it would be possible to further improve their UV blocking properties. , it is possible to largely prevent the contents from deteriorating even under long-term storage.

Since it causes discoloration of indoor fixtures such as cabinets and furniture, it is necessary to minimize its transmission or completely block it.
It is well known that by mulching with a transparent coating material that substantially blocks the transmission of ultraviolet light of 70 nm or less, it is possible to promote the growth of many useful plants and to harvest high-quality crops early and in large quantities. For example, JP-A No. 33-/Nige ssA
Publication No.).

Currently, in the flame industry, ultraviolet absorbers and the like are generally added and used for this purpose. However, Towara's ultraviolet absorbers are generally expensive, and the application process is complicated, and these compounds generally have high sublimation properties and many have poor thermal stability. Troubles often occur during the application process and molding process, and when used in food containers and packaging, there is a risk of transfer to the contents, which is not necessarily desirable.

<Problems to be Solved by the Invention> In view of the current situation, the present inventors have made extensive studies and have invented a thermoplastic polyester resin composition in which a compound having a naphthalenetetracarboxylic acid skeleton is added in an amount effective for blocking ultraviolet rays. I did it (Tokugan Showotsu Koko 5 oztq).

Based on this result, the present inventors conducted further extensive studies and found that naphthalenetetracarboxylic acid diimide compound, which is a particularly novel compound among naphthalenetetracarboxylic acid derivatives, has excellent ultraviolet blocking properties. It was discovered that polyester materials are excellent in copolymerizability, thermal stability, non-coloring properties, etc., leading to the present invention.

Means for Solving the Problems> That is, the present invention resides in a naphthalenetetracarboxylic acid diimide compound represented by the following general formula (1).

Indicates an integer of 20. ), or 8CH2+n (n is /~
Indicates an integer of da. Further, the phenylene group is bonded to the nitrogen atom forming the imide ring in formula (1). ), R represents a hydrogen atom or an alkyl group having 7 to g carbon atoms. However, when X is (), R represents an alkyl group having from co to g carbon atoms.

When X is (), R represents an alkyl group having 2 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, specifically ethyl, n-propyl, isopropyl, lupustyl, tert. -butyl group.

If X is +CH2+m or (miEcH2-),
R represents a hydrogen atom or an alkyl group having l-carbon atoms;
Preferably it is a hydrogen atom or an alkyl group having /-f carbon atoms, specifically methyl, ethyl, n-propyl,
These are isopropyl, n-butyl, and tert-butyl groups.

The naphthalenetetracarboxylic acid diimide compound of the present invention has, for example, naphthalene-/,Q, g-tetracarboxylic acids and general formula (I[) (wherein XSR is the same as in formula (1), R ', R'' is a hydrogen atom or the number of carbon atoms is /
- represents an alkyl group of ff. ) It can be produced by an imidization reaction with an aminocarboxylic acid represented by the following formula, and has two imide bonds in the molecule.

Naphthalene-/,'I,! , g-tetracarboxylic acids also include their ester forms and anhydrides.

An example of the above imidization reaction will be specifically shown below. Naphthalene-/,'I,! , the molar ratio of g-tetracarboxylic acid to aminocarboxylic acid is q/: 1.03.0, and the mixture is heated and stirred in an acetic acid solvent. ;
, g-tetracarboxylic acid and the generated naphthalenetetracarboxylic acid diimide compound are substantially insoluble in acetic acid, so the reaction proceeds in a suspension system throughout. The reaction temperature can be set arbitrarily between room temperature and the boiling point of acetic acid, but in order to obtain a practical reaction rate, it is preferable to carry out the reaction at the boiling point of acetic acid. In this case, the reaction time is 3 to lθ hours, during which time the water produced by the reaction may be removed from the reaction system or refluxed into the reaction system. If necessary, it is possible to carry out the reaction under pressure and at a higher reaction temperature, but in order to avoid deterioration or decomposition of the reaction products, 2! ;0'Ct- It is preferable not to exceed.

After the acetic acid is removed in a furnace, the suspended reaction solution obtained by this reaction is suspended washed with a suitable solvent such as water, acetone, alcohol, acetic acid, etc. in order to remove excess aminocarboxylic acid, and then filtered. By removing the solvent by drying or the like, the desired naphthalenetetracarboxylic acid diimide compound is obtained. Needless to say, the method for obtaining the target product is not limited to the reaction purification method described above, and any conventionally known useful method can be selected.

The naphthalenetetracarboxylic acid diimide compound of the present invention thus obtained is useful as an ultraviolet absorber, and has very excellent properties, particularly as a constituent of polyester materials.

The excellent characteristics are listed below: [1]
Naphthalene-i, lI,! Based on the basic skeleton of r,g-tetracarboxylic acid, near ultraviolet region (3g.

The present invention can block harmful ultraviolet light that cannot be blocked by polyesters such as polyethylene terephthalate.

(2) Naphthalene-/,'l,3. Since the thermal instability of g-tetracarboxylic acid has been greatly improved by diimidation, for example, the polymerization temperature of polybutylene terephthalate (,21I
Problems such as decomposition and deterioration do not occur even if the material is kept for a long time at temperatures around It is possible to provide a polyester material etc. that has excellent ultraviolet blocking properties and is free from concerns such as sublimation, bleed-out, and elution, which tend to be problems with chemicals.

(4) When adding a colorless imide compound with excellent ultraviolet blocking properties to a thermoplastic polyester resin because it hardly absorbs visible light of qoonm or more, the amount of addition should be 100% of the thermoplastic polyester resin. Weight part per p,
o, ooi parts by weight or more. When the amount is less than 0.00/part by weight, no effective ultraviolet a blocking effect can be obtained. A particularly preferable addition amount is 0.07 to 70 parts by weight.

These diimide compounds may be added at any stage of polyester production, and even when added at any stage before molding, they can similarly exhibit the ultraviolet blocking effect.

That is, it may be added at any stage until the completion of molding of polyester, for example, before the start of the polycondensation reaction, during the polycondensation reaction, after the end of the polycondensation reaction, in the form of powder, during the molding stage, etc.

As the thermoplastic polyester in the present invention, Tele7
Aromatic dicarboxylic acids such as curric acid, isophthalic acid, fucuric acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid and their ester formation products, and nuclear hydrogenated compounds of the above aromatic dicarboxylic acids such as hexahydroterephthalic acid. certain alicyclic dicarboxylic acids and their esters; aliphatic dicarboxylic acids and their esters, such as succinic acid, adipic acid, sebacic acid, and azelaic acid; unsaturated dicarboxylic acids, such as fumaric acid and cucarboquine cinnamic acid; A polyester obtained from one or more dicarboxylic acid components represented by an ester forming body and a glycol component mainly composed of ethylene glycol, especially polyethylene terephthalate, but these polyesters can be used as a third component. , 20 mol % or less of the above dicarboxylic acids other than terephthalic acid.

'81. In addition, this polyester contains diethylene glycol, in addition to ethylene glycol, as a glycol component.
trimethylene glycol, tetramethylene glycol,
aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanesimethanol,
λ1. ! - bisphenol derivatives, such as bis(t'-β-hydroxyethoxyphenyl)propane, bis-(1Ir-β-hydroxyethoxyphenyl)sulfone,
Furthermore, it may be a product obtained by copolymerizing polyethylene glycol, polytetramethylene glycol, etc. with a molar ratio of less than aO of the total glycol component, or a polyester obtained by copolymerizing an oxyacid component such as glycolic acid or hydroxybenzoic acid. It's okay. As long as the primary polyester remains substantially linear, trifunctional or higher functional compounds such as pentaerythrol, trimethylolpropane, trimellitic acid, trimesic acid, pyromellitic acid, and 0-benzoylbenzoic acid may be used. Monofunctional compounds such as may be copolymerized.

Further, in addition to the above-mentioned polyester, a blend of other thermoplastic resins such as polybutylene terephthalate, polyethylene naphthalate, polyester elastomer, polycarbonate, etc. may be used.

The polyester used in the present invention has an intrinsic viscosity of 0.3-
2.3 is preferred, and more preferably O06 to 8 is used. The viscosity of polyester is important, for example, when manufacturing blow molded bodies, especially in relation to the molding method. Particularly when extrusion blow molding is used to obtain a substantially non-oriented hollow molded body, it is necessary to maintain the fluidity of the molten polyester above a certain level in order to prevent drawdown, although this depends on the capacity of the blow molded body. In general, a polyester having an intrinsic viscosity of 0.7 or more, preferably 0.3 to 6 is used. In addition, in stretch blow molding, extrusion molding to obtain a film by -axial or biaxial stretching after sorting, and injection molding to obtain molded products in various forms, the viscosity is relatively low compared to extrusion blow molding. Polymers can also be used, and generally those with an intrinsic viscosity of O.S or higher, preferably θ, 6 to 2 are used, but depending on the required physical properties of the molded product, even higher viscosity polyesters may be used. Ru.

The polyester resin composition with excellent ultraviolet blocking properties obtained in the present invention is melt-molded and molded into a molded article. In this case, all melt molding methods commonly used for polyester can be applied. Specifically, blow molding methods such as the usual extrusion blowing method, injection blowing method, and cold parison method in which a preform is biaxially stretched after reheating achieve excellent ultraviolet blocking properties, gas blocking properties, toughness, and chemical resistance. At the same time, it is possible to obtain a hollow molded body with a high-class glass-like transparency. It is particularly suitable for containers for alcohol, wine, cosmetics, and medicine. After thinning by extrusion molding, it is made into a -axially or biaxially stretched film or a laminated film with other resins for packaging of general foods, medicines, cosmetics, etc., as well as for window pasting and mulching used in agriculture and horticulture. It is particularly preferably used as a covering material, and is also preferably used as molded products of various shapes by injection molding.

Of course, the use of the naphthalenetetracarboxylic acid diimide compound of the present invention is not limited to ultraviolet absorbers or polyester materials to which fL is added, and it may be copolymerized with nylon etc. or with other polymers. It may be used in the same way as a general ultraviolet absorber. Furthermore, it can also be used as a constituent of new polymer materials such as so-called engineering plastics.

<Example> The present invention will be explained below using examples.

The measuring device used in this example is shown below.

0 melting point The apex of the endothermic peak when the temperature was raised at 16° C./min using a Seiko Electronics DSC λθ type was taken as the melting point.

OIR spectrum was measured by the KBr tablet method using a JASCO Corporation A-3IR spectrophotometer.

o H-NMR JEOL JNM-GX 2? OFT-NMR was used.

o HPLC (High Performance Liquid Chromatography) Takafusa Seisakusho LC-4'A system is used, and the column is Mitsubishi Kasei MCI.
Using GEL 0DS-IHU 3! ; Measured using an Onm UV detector.

0 intrinsic viscosity Phenol-tetrachloroethane (zo7s;.

weight ratio), 30°C, 1. It was measured at a concentration of o97dl.

0 Ultraviolet transmittance was measured by a conventional method using a Hitachi spectral photometer model Jlθ.

Naphthalene-/, 4', j, Za- used in this example
Tetracarboxylic acid (NTCA) was a commercially available purified product. The purified product does not have a melting point up to 3A; O'C,
Elemental analysis shows that carbon j1. uff%, 2.4 g of hydrogen, IR (Figure-'), NMR (Figure-2), ) (P
From the results of LC (Figure 3), the main components are naphthalene-/,
'1. ! It was identified as g-tetracarboxylic acid, and the purity is believed to be about 9S%.

Most of the subcomponents are naphthalene-/, 'l, j, g
-Tetracarboxylic acid-cannot be considered an anhydride.

Example/ Naphthalene-/, 'I, g-tetracarboxylic acid 30
, lI fl (0.1 mol) and the reagent 39.14 (0.211 mol) of ethyl p-aminobenzoate were weighed into a 500 ml round bottom flask equipped with a stirrer and a reflux condenser, and 30% of reagent grade acetic acid was added. 'After adding 1ml, N2
Under a seal, the boiling point of acetic acid (77g℃)'! The temperature was raised at , and the reaction was carried out with stirring for 7 hours.

After the reaction was completed, it was allowed to cool and filtered under reduced pressure using A2B F paper, and then evaporated twice with 5OO- acetone and twice with fl demineralized water.
Wash by hanging, filter, dry again, and obtain the target compound (A)'
I got it. The yield was &left, /9 (yield: 9 g).

The obtained compound had a melting point of 3g2°C by DSC and an elemental analysis of carbon A7. Section 7, 30 g of hydrogen, nitrogen gas, g section, IR (Fig. 5) and NMR (Fig. 5)
) N, N' having the following structural formula together with the analysis results of
-bis(guethylcarboxyphenyl)-naphthalene-/, 'I, left, identified as g-tetracarboxydiimide.

Example 1 Example 1 except that ethyl p-aminobenzoate was replaced by /-monoaminododecanoic acid A; The reaction and purification were carried out in the same manner as above to obtain the target compound (B).

The yield was Ajt, Ag (yield: 99).

The obtained compound has a melting point of 229°C by DSC, and elemental analysis shows that carbon: 6g, 97%, hydrogen: 7.7%, nitrogen:
N,N'-bis(//-carboxyundenyl)-naphthalene-i having the following structural formula in conjunction with the analysis results of Section 9 and IR (Figure 6) and NMR (Figure 7) ,
It was identified as lI,h,g-tetracarboxydiimide.

Example 3 Same as Example except that 34.3 g (0.2'I mol) of p-aminophenyl acetic acid was used instead of ethyl p-amino-7benzoate and ethanol was used instead of acetone. Reaction and purification were performed to obtain the target compound (C). The yield was 96 on the left.

The compound f′ obtained had a melting point of yo by DSC.

``C1 elemental analysis shows carbon A 7.77%, hydrogen 3.2%,
Nitrogen S, Mu] was identified by IR (Figure-g) and NMR phenyl)-naphthalene-/, 11, t, g-tetracarboxyne diimide f'.

Example 100 g of dimethyl cutylephthalate, naphthalene, 6-
Dimethyl dicarboxylate o, lIg, diimide compound (A) obtained in Example//θ, /11 ethylene glycol 70fi, manganese acetate', water J, o x g'
6. After weighing all the ingredients into a soup glass reactor equipped with a stirrer and a distillation tube, the temperature was raised to 760°C, dimethyl terephthalate was dissolved under stirring, and the reaction product was heated to 230'C while distilling methanol etc. The transesterification reaction was carried out for the specified time. Here, orthophosphoric acid 0.0.2 g, germanium dioxide 0.02 fl
was added, the temperature was raised again, and the pressure inside the reaction system was gradually reduced.
Finally, a polycondensation reaction was carried out at 270° C. under a vacuum of /torr for a measured time to obtain a transparent polyester having an intrinsic viscosity of 0.65.

The polyester is melt press-molded and then rapidly cooled to a wall thickness of 3 left θ.
A sheet of μ was molded. 370 nm of the sort and 3
The light transmittance at kOμm is determined by
．． / Showed the person in charge. A light transmittance chart is shown in Figure-IO.

Example S Dimethyl terephthalate ggg, naphthalene-core O-dicarboxylic acid dimethyl o, q g, diimide compound (A) obtained in Example 1 was added to 0. /7ji, /, gobutanediol soy, titanium tetraphthoxide o, i lI
After weighing g together into a reactor similar to the example,
After raising the temperature to iso℃ and dissolving dimethyl terephthalate under stirring, the reaction product methanol etc. should be distilled out.
The temperature was gradually raised to 10°C, and the transesterification reaction was carried out for a total of λ and S time.

Subsequently, the temperature was raised again and the pressure inside the reaction system was gradually reduced, and finally, a polycondensation reaction was carried out for 3 hours under vacuum at 2 II j °C and /torr until the intrinsic viscosity was reduced to o, g o
A crystallized polyester was obtained. The polyester was melt press-molded and then rapidly cooled to form a transparent sheet with a wall thickness of 30 μm. The light transmittance of the sheet at 3 nm and 3 g onm was 0, ti, and 0, i%, respectively.

Example 6 In place of the diimide compound (A), the diimide compound (B) obtained in Example 1 was used at a concentration of 0. Transesterification and polycondensation reactions were carried out in the same manner as in Example except that :l 39 was used to obtain a transparent polyester having an extreme viscosity of 0.4&.

The polyester is melt-pressed and then rapidly cooled to a wall thickness of 2K.
A sheet of Oμ was molded. The light transmittance of the sort at 370 nm and 3 g Onm was 0.7 and 0.1, respectively.

Example 7 Transesterification and polycondensation reactions were carried out in the same manner as in Example G, except that the diimide compound (c) obtained in Example 3 was used in place of the diimide compound (A), and the intrinsic viscosity was determined. A transparent polyester with O, t, and S was obtained.

After the polyester is completely melt press-molded, it is rapidly cooled to a wall thickness of 350 mm.
A sheet of μ was formed. 370 nm of the sheet and 3
The light transmittance at g Onm is θ0.2
and θ, O relation.

[Brief explanation of the drawing]

Figures 11 and 3 are NTCA's IR. NMR, HPLC chart, Figure-71 Figure-S shows IR and NMRf of compound (A) obtained in Example/
Figures 6 and 7 show I of compound (B) obtained in Example 7.
R and NMRJ', Figure 31 Figure 9 is a chart of IRl and NMR of compound (C) obtained in Example 3. Moreover, FIG. 70 shows the light transmittance of the polyester resin composition obtained in Example, where the vertical axis represents the transmittance and the horizontal axis represents the wavelength.

Claims (4)

[Claims] (1) A naphthalenetetracarboxylic acid diimide compound represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (1) In the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (m indicates an integer from 11 to 20), or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n indicates an integer from 1 to 4. Also, the phenylene group is (I
) is bonded to the nitrogen atom forming the imide ring in the formula. ), and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, when X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R represents an alkyl group having 2 to 8 carbon atoms. (2) Naphthalene-1,4,5,8-tetracarboxylic acids and general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (II) In the formula, X is ▲ There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼(m indicates an integer from 11 to 20), or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(n indicates an integer from 1 to 4.Also, the phenylene group is (II ), and R, R', and R'' are hydrogen atoms or have 1 to 8 carbon atoms.
represents an alkyl group. However, when X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R represents an alkyl group having 2 to 8 carbon atoms. General formula (I) characterized by imidization reaction with aminocarboxylic acids represented by (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼・・・・・・(I) [(I) In color, X and R has the same meaning as in formula (II).
] A method for producing a naphthalenetetracarboxylic acid diimide compound represented by (3) An ultraviolet absorber comprising a naphthalenetetracarboxylic acid diimide compound represented by the general formula (I) according to claim 1. (4) A polyester resin composition comprising a thermoplastic polyester resin and a naphthalenetetracarboxylic acid diimide compound represented by the general formula (I) according to claim 1.