JP2003055311A - Benzoic acid glycerol ester, plasticizer comprising the same and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain benzoic acid glycerol ester useful as a plasticizer for a polyvinyl chloride, polylactic acid, etc. SOLUTION: This benzoic acid glycerol ester is represented by general formula (1) or general formula (2) (R<1> and R<2> are each a 4-18C alkyl group; R<3> is a 1-8C alkyl group or a phenyl group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel glycerin ester of benzoic acid, a plasticizer comprising the ester, and a resin composition containing the ester.

[0002]

2. Description of the Related Art Polyvinyl chloride can be variously changed in its properties by being combined with a plasticizer and has a wide range of application fields such as pipes, window frames, films and hoses.
The most commonly used plasticizer for polyvinyl chloride is phthalate ester, which has heat resistance, weather resistance, and
It is still insufficient in terms of light resistance and migration resistance. Phthalates are substances suspected of being endocrine disruptors and are toxic to boys according to the US National Toxicology Program (NTP) in the final report. Polylactic acid, which is a typical biodegradable plastic, is a hard crystalline resin that is difficult to use alone. Therefore, it is used by being modified into a resin that can be easily molded by copolymerization or the like. Phthalic acid esters and adipic acid esters have been studied as plasticizers for polylactic acid, but there is a problem of impairing transparency, which is a characteristic of polylactic acid (Shimadzu review 54
Vol. 1, 55).

[0003]

The present invention has been made under such circumstances, and provides a novel glycerin ester of benzoic acid, a plasticizer comprising the ester, and a resin composition containing the ester. That is the purpose.

[0004]

The present inventor completed the present invention as a result of diligent efforts to solve the above-mentioned problems of phthalic acid ester and to develop a novel plasticizer which does not impair the transparency of polylactic acid. Came to. That is, the present invention provides the general formula (1) or the general formula (2).

[Chemical 3]

[Chemical 4] (In the formula, R ¹ and R ² each represent an alkyl group having 4 to 18 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group.) Glycerin of benzoic acid With respect to 100 parts by mass of an ester, a plasticizer and a resin composed of a glycerin ester of benzoic acid represented by the general formula (1) and / or the general formula (2), the general formula (1) and / or the general formula (2) Represented glycerin ester of benzoic acid 5
The present invention relates to a resin composition containing 80 parts by mass.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formulas (1) and (2), R ¹ and R ² are alkyl groups having 4 to 18 carbon atoms (straight chain or branched alkyl groups), and preferably having carbon atoms. 6
~ 14 alkyl groups. Examples of the alkyl group having 4 to 18 carbon atoms include n-amyl group, i-amyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group and i-octyl group. , 2-ethyl-hexyl group, n-nonyl group, i-nonyl group, n-decyl group, i-decyl group, n-undecyl group, i-undecyl group, n-decyl group, i-decyl group, n- Tridecyl group,
i-tridecyl group, n-tetradecyl group, i-tetradecyl group, n-pentadecyl group, i-pentadecyl group, n
-Hexadecyl group, i-hexadecyl group, n-heptadecyl group, i-heptadecyl group, n-octadecyl group, i-octadecyl group, etc. can be illustrated. Specific examples of the alkyl group having 1 to 8 carbon atoms (straight or branched alkyl group) for R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Butyl group,
sec-butyl group, tert-butyl group, n-amyl group, i-amyl group, n-hexyl group, i-hexyl group,
n-heptyl group, i-heptyl group, n-octyl group, i
Examples thereof include a --octyl group and a 2-ethyl-hexyl group.

Specific examples of the glycerin ester of benzoic acid represented by the general formula (1) of the present invention include glycerin-
1-benzoate-2,3-dilaurate, glycerin-1-benzoate-2,3-di (2-ethylhexanoate), glycerin-1-benzoate-2,3-dioctylate, glycerin-1-benzoate-2, Three
-Dinonylate, glycerin-1-benzoate-2-
Examples thereof include laurate-3- (2-ethylhexanoate) and glycerin-1-benzoate-2-laurate-3-caprylate. Examples of the glycerin ester of benzoic acid represented by the general formula (2) include glycerin-2-
Benzoate-1,3-dilaurate, glycerin-2
-Benzoate-1,3-di (2-ethylhexanoate), glycerin-2-benzoate-1,3-dioctylate, glycerin-2-benzoate-1,3-dinonilate, glycerin-2-benzoate-1-laurate Examples thereof include -3- (2-ethylhexanoate) and glycerin-2-benzoate-1-laurate-3-caprylate.

General formula (1) / or general formula (2) of the present invention
The method for producing the glycerin ester of benzoic acid represented by is not particularly limited, but it can be produced, for example, by the following method. 1. A method of heating and dehydrating glycerin, fatty acid and benzoic acid in the presence of an acid catalyst. As the fatty acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,
Undecyl acid, lauric acid, myristic acid, stearin, etc. are mentioned. Acid catalysts include hydrochloric acid, sulfuric acid, p-
Toluenesulfonic acid, acidic ion exchange resin, etc. may be mentioned. The reaction temperature is 110 to 300 ° C., preferably 160
~ 210 ° C. Examples of the solvent for azeotropically dehydrating the produced water include toluene and xylene. 2. A method of transesterifying a fat and oil with benzoic acid or a benzoic acid ester. As the fats and oils, fats and oils having a small content of unsaturated fatty acids such as coconut oil and palm kernel oil are preferable. The reaction temperature is 100 to 300 ° C., preferably 140 to 250.
℃. 3. Above 1. And 2. A method of synthesis using an enzyme such as lipase in the reaction of.

The resin for which the plasticizer comprising the glycerin ester of benzoic acid represented by the general formula (1) and / or the general formula (2) of the present invention can be used is not particularly limited, but polychlorinated. Vinyl, vinyl chloride-vinyl acetate copolymer, polylactic acid and the like are preferable. The blending amount of the glycerin ester of benzoic acid represented by the general formula (1) and / or the general formula (2) is 5 to 80 parts by mass of the glycerin ester of benzoic acid with respect to 100 parts by mass of the resin, and preferably 10 to 60 parts by mass. As a blending method, a method of melting and blending a resin with a glycerin ester of benzoic acid represented by the general formula (1) and / or the general formula (2), a resin and the general formula (1) and / or the general formula ( A method in which the glycerin ester of benzoic acid represented by 2) is blended as a solution of methylene chloride or the like can be mentioned. At the time of blending, an antioxidant, a flame retardant, an ultraviolet absorber, a stabilizer, a colorant, a foaming agent, an antistatic agent and the like can be added.

Examples of antioxidants include phenolic antioxidants and phosphorus antioxidants. As a phenolic antioxidant, 2,6-di-t-butyl-4-
Methylphenol, n-octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2-t-butyl-6- (3-t-butyl-2)
-Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,
5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ] 1, 6
-Hexanediol-bis- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
3,9-bis [1,1-di-methyl-2- [β- (3-
t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris (3,
5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris (4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate and the like can be used. Examples of phosphorus-based antioxidants include tris (nonylphenyl) phosphite and tris (2,4-di-t).
-Butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di- Phosphite, bis (2,4,6-tri-t-butylphenyl)
Pentaerythritol-di-phosphite, Methylenebis (2,4-di-t-butylphenyl) octylphosphite, Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phospho Knight, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite and the like can be used.

Examples of the ultraviolet absorber include the followings. Hydroquinone-based UV absorbers include hydroquinone and hydroquinone disalicyle
And salicylic acid-based UV absorbers include phenyl salicylate, paraoctyl phenyl salicylate, and benzophenone-based UV absorbers such as 2-hydroxy-4.
-Methoxybenzophenone, 2-hydroxy-4-n-
Octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-hydroxybenzophenone, 2,2'-hydroxy-4,4
′ -Dimethoxybenzophenone, 2-hydroxy-4-
Benzoyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-Methoxy-5-sulfone benzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2,2 '
-Hydroxy-4,4'-dimethoxy-5-sodium sulfobenzophenone, 4-doteciloxy-2-hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, and benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5)
′ -Methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2′-hydroxy-5′-
Methylphenyl) -5,6-dichlorobenzotriazo-
2- (2'-hydroxy-5'-methylphenyl)
-5-ethyl sulfone benzotriazole, 2- (2 '
-Hydroxy-5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5 '
-Tert-butylphenyl) benzotriazole, 2- (2
′ -Hydroxy-5′-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dimethylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dimethyl (Phenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3 ', 5'-dimethylphenyl) ) -5
-Methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazol ethyl ester, 2- (2'-hydroxy-3'-methyl-5)
′ ′ -Tertiary butylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-ditertiary butylphenyl) -5-chloro-benzotriazole, 2- (2'-
Hydroxy-5'-methoxyphenyl) benzotriazol, 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'-cyclohexylphenyl) ) Benzotriazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazol butyl ester, 2- (2'-hydroxy-3', 5'-
Dichlorophenyl) benzotriazole, 2- (2'-
Hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-ethylsulfone benzotriazole, 2- (2 '-Hydroxy-5'-phenylphenyl) benzotriazole, 2- (2'-hydroxy-4)
′ -Octoxyphenyl) benzotriazole, 2-
(2'-hydroxy-5'-methoxyphenyl) -5-
Methylbenzotriazole, 2- (2'-hydroxy-
5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2- (2'-acetoxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-diter Charly butylphenyl) -5
-Chlorobenzotriazole and the like can be used.

As the colorant, titanium oxide, zinc white, lead white, calcium carbonate, gypsum, precipitated silica, carbon black, red iron oxide, aluminum powder, bronze powder, mica, molybdenum red, cadmium yellow, yellow lead, titanium yellow. Inorganic pigments such as chrome oxide green and ultramarine blue: Permanent red 4R Hansa Yellow 10G, benzi yellow GR, permanent carmine FB, phthalocyanine blue B, phthalocyanine green, and other organic pigments can be used. As the foaming agent, azobisisobutyronitrile or the like can be used. As the antistatic agent, an anion activator, a cation activator, a nonionic activator, an amphoteric activator and the like can be used. As the flame retardant, tetrachlorophthalic acid, tetrabromophthalic acid, tetrabromobisphenol A, antimony trioxide, chlorinated paraffin and the like can be used.

[0012]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 In a 300 ml separable flask equipped with a Dean Stark trap, a thermocouple, and a stirrer, glycerin 9.2 was added.
g, benzoic acid 12.8 g, lauric acid 40.8 g, concentrated sulfuric acid 50 mg and toluene 50 ml were charged, and the mixture was heated at 160 ° C. for 8 hours.
The mixture was heated and stirred at 210 ° C. for 12 hours. While heating, toluene was refluxed to remove water generated by the reaction. After the reaction was completed, the product was washed twice with 200 ml of water containing 5 g of sodium hydrogen carbonate, then once with water, and dried using magnesium sulfate. The yield of the product (abbreviated as plasticizer A) was 51 g (94% yield). A part of the product was purified by thin layer chromatography and measured by gel permeation chromatography (GPC) and nuclear magnetic resonance spectrum (NMR).
84% of the product is glycerin-1-benzoate-
It was a mixture of 2,3-dilaurate and glycerin-2-benzoate-1,3-dilaurate (50:50). The remaining 18% was a mixture of 1-benzoate-3-laurate-1-propene and 1-laurate-3-benzoate-1-propene (50:50). (Measurement data) Nuclear magnetic resonance spectrum (NMR) = CDCl ₃ ¹ H NMR (270 MHz): δ0.82-0.91,1.10-1.38,1.50-1.69,2.24
-2.50,4.10-4.68,7.40-7.65,7.98-8.13 ¹³ C-NMR (68MHz): 13.960,22.615.24.873,29.423,31.871,
34.245,62.138,62.93,68.922,128.402,129.712,133.14
9,165.972,172.780 Infrared absorption spectrum (cm ^-1 ) 1732 (C = O) Mass spectrometry (DI-MS): [m / e] 560 (22%)

Example 2 Glycerin 9.2 was placed in a 300 ml separable flask equipped with a Dean Stark trap, a thermocouple and a stirrer.
g, benzoic acid 12.8 g, 2-ethylhexanoic acid 30.
Charge 3g, concentrated sulfuric acid 40mg, toluene 50ml, 1
The mixture was heated and stirred at 60 ° C. for 8 hours and then at 210 ° C. for 12 hours. While heating, toluene was refluxed to remove water generated by the reaction. After the reaction was completed, the product was washed twice with 200 ml of water containing 5 g of sodium hydrogen carbonate, then once with water, and dried using magnesium sulfate. The yield of the product (abbreviated as plasticizer B) was 45.7 g (yield 91%). Part of the product was purified by thin layer chromatography and gel permeation chromatography (G
PC) and nuclear magnetic resonance spectrum (NMR) showed that 84% of the product was glycerin-1-benzoate-2,3-di (2-ethylhexanoate) and glycerin-2-benzoate- It was a mixture (50:50) of 1,3-di (2-ethylhexanoate). The remaining 16% is 1-benzoate-3- (2
-Ethylhexanoate) -1-propene and 1- (2
-Ethylhexanoate) -3-benzoate-1-propene mixture (50:50). (Measurement data) Nuclear magnetic resonance spectrum (NMR) = CDCl ₃ ¹ H NMR (270 MHz): δ0.82-0.98,1.10-1.75,2.19-2.38,3.95
-4.75,7.10-7.60 7.90-8.09 ¹³ C-NMR (68MHz): 11.644,13.754,22.524,25.261,29.506,
31.525,47.178,62.08,63.062,69.013,69.994,128.377,1
29.704,133.141,165.988,175.657 Infrared absorption spectrum (cm ^-1 ) 1736 (C = O) Mass spectrometry (DI-MS): [m / e] 448 (11%)

Example 3 (Blend to Vinyl Chloride-Vinyl Acetate Copolymer) Vinyl chloride-vinyl acetate was used with methylene chloride as a solvent.
(9: 1) copolymer (Mn22000 manufactured by Aldrich)
100 parts by mass of the plasticizer A of Example 1 and 10 to 50 parts by mass of the plasticizer B of Example 2 were respectively blended to form a cast film and dried with a vacuum dryer. It was measured. The results are shown in Table 1. In the table, ○ indicates transparent, Δ indicates slightly cloudy, and × indicates cloudy. Table 1
Therefore, the plasticizer A and the plasticizer B have a remarkable effect of lowering the glass transition temperature as compared with the case where the plasticizer is not added,
Further, it was found that the compound retained transparency, and it was found that this compound has excellent performance as a plasticizer.

[0015]

[Table 1]

Example 4 (Blend to polylactic acid) Using methylene chloride as a solvent, 100 parts by mass of polylactic acid (Mn 20000 manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with Plasticizer A of Example 1 and Plasticizer B of Example 2. 10 to 50 parts by mass of each was blended to form a cast film, which was dried with a vacuum dryer, and then the glass transition temperature and the transparency were measured. The results are shown in Table 1. In the table, ○ indicates transparent, Δ indicates slightly cloudy, and × indicates cloudy. It can be seen from Table 2 that the plasticizer A and the plasticizer B have a remarkable effect of lowering the glass transition temperature as compared with the case where no plasticizer is added, and further retain transparency, and this compound has excellent performance as a plasticizer. Was found to have.

[0017]

[Table 2]

[0018]

EFFECT OF THE INVENTION General formula (1) or general formula (2) of the present invention
The glycerin ester of benzoic acid represented by the formula (3) has a structure in which a part of natural fats and oils is replaced with benzoic acid existing in nature, and can be used as a harmless plasticizer. Glycerin ester of benzoic acid of the present invention is a plasticizer having excellent heat resistance, weather resistance, light resistance and migration resistance, and a plasticizing effect, and is a garbage bag which is an application field of biodegradable plastics such as polylactic acid, It is useful as a plasticizer used for molding materials such as toys, disposable gloves for cooking, medical materials, and water hoses, which are applications such as food trays and polyvinyl chloride.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00

Claims (4)

[Claims] 1. A general formula (1) or a general formula (2): [Chemical 2] (In the formula, R ¹ and R ² each represent an alkyl group having 4 to 18 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group.) Glycerin of benzoic acid ester. 2. A plasticizer comprising a glycerin ester of benzoic acid represented by the general formula (1) and / or the general formula (2). 3. The general formula (1) with respect to 100 parts by mass of the resin.
And / or a resin composition containing 5 to 80 parts by mass of a glycerin ester of benzoic acid represented by the general formula (2). 4. The resin is polyvinyl chloride, vinyl chloride-
The resin composition according to claim 3, which is at least one resin selected from a vinyl acetate copolymer and polylactic acid.