JP2008031069A - Benzyl diglycerol acetate and polyester resin composition containing the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel compound having the excellent function as a polyester-based resin plasticizer. <P>SOLUTION: A benzyl diglycerol acetate compound represented by the chemical formula (I): (wherein A is CH<SB>3</SB>CO-, or R<SP>1</SP>C<SB>6</SB>H<SB>4</SB>CH<SB>2</SB>- (wherein R<SP>1</SP>is a hydrogen, a 1-3C alkyl or hydroxyl)), and B is R<SP>2</SP>C<SB>6</SB>H<SB>4</SB>CH<SB>2</SB>- (wherein R<SP>2</SP>is a hydrogen, a 1-3C alkyl or hydroxyl) is provided. A polyester resin composition containing the compound is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel benzyl diglycerin acetate compound and its use as a plasticizer.

  Polyester resins are provided with flexibility by containing a plasticizer, and are used in various applications.

  Known plasticizers include phthalic acid, adipic acid, phosphoric acid, and polyester compounds. In recent years, plasticizers that reduce the burden on the environment have been developed due to increasing awareness of problems with the human body and the natural environment. Plasticizers that can be used for biodegradable plastics such as polylactic acid have also been developed. ing. As these plasticizers, ester compounds such as acetylated tributyl citrate (for example, Non-patent Document 1), monoalkyl diallyl triglyceride (for example, Patent Document 1) and diglycerin tetraacetate (for example, Patent Document 2) are disclosed. ing.

However, when these plasticizers are used, it has been pointed out that the plasticizer volatilizes from the resin during processing or when used at high temperatures, resulting in a decrease in function.
JP 2003-221462 A JP 2003-231798 A JOURNAL OF APPLIED POLYMER SCIENCE 90 p.1731 (2003)

  This invention is made | formed in view of the said situation, and it aims at providing the novel compound which has the effect | action outstanding as a plasticizer of a polyester-type resin.

（式中、ＡはＣＨ_３ＣＯ−、またはＲ^１Ｃ_６Ｈ_４ＣＨ_２−（式中、Ｒ^１は、水素原子、炭素数１〜３のアルキル基またはヒドロキシル基を表す）；
ＢはＲ^２Ｃ_６Ｈ_４ＣＨ_２−（式中、Ｒ^２は、水素原子、炭素数１〜３のアルキル基またはヒドロキシル基を表す））を提供するものである。 That is, the present invention provides a benzyl diglycerin acetate compound represented by the following chemical formula (I):

(In the formula, A represents CH ₃ CO—, or R ¹ C ₆ H ₄ CH ₂ — (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyl group);
B provides R ² C ₆ H ₄ CH ₂ — (wherein R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group).

  The benzyl diglycerin acetate compound of the present invention is a novel compound, and when used in a polyester resin composition, exhibits low volatility and high plasticizing performance, less bleed out from the resin, and transparent resin Does not disturb sex.

The novel benzyl diglycerin acetate compound provided by the present invention is represented by the following chemical formula (I).

In the above general formula (I), A represents CH ₃ CO—, or R ¹ C ₆ H ₄ CH ₂ — (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyl group. ).
The hydroxyl group constituting R ¹ may be an ester. Preferred R ¹ is a hydrogen atom.

In the above general formula (I), B is R ² C ₆ H ₄ CH ₂ — (wherein R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyl group).
The hydroxyl group constituting R ² may be an ester. Preferred R ² is a hydrogen atom.

である。 In particular, among the benzyl diglycerin acetate compounds represented by the chemical formula (I), preferred compounds are:

It is.

The benzyl diglycerin acetate compound represented by the chemical formula (I) can be synthesized through the following reaction pathway.

  As diglycerin (the above-mentioned compound (1)), a commercially available product, for example, a material readily available from Tokyo Chemical Industry Co., Ltd. can be used as it is.

The compound (2) is, for example, diglycerin (compound (1) above) and benzyl chloride optionally having substituent R ¹ at a molar ratio of 1: 1.2 at 60 ° C. in anhydrous DMF. It is obtained by reacting for hours.

  The compound (3) can be obtained, for example, by reacting the compound (2) and acetic anhydride in a molar ratio of 1: 7 in pyridine at room temperature for 18 hours.

For example, the compound (4) may be prepared by using diglycerol (the above compound (1)) and benzaldehyde optionally having substituents R ¹ and / or R ² in a molar ratio of 1:10 as p as an acid catalyst. -Obtained by reacting in a DMF-benzene mixed solvent at 110 ° C for 11 hours in the presence of toluenesulfonic acid.

  The compound (5) can be obtained, for example, by reacting dibenzylideneglycerin (the compound (4)) with diisobutylaluminum hydride as a reducing agent at a molar ratio of 1: 5.6 at room temperature for 18 hours.

  The compound (6) can be obtained, for example, by reacting 1,1′-O-dibenzylglycerin (the compound (5)) and acetic anhydride in a molar ratio of 1:10 in pyridine at room temperature for 18 hours. .

  The benzyl diglycerin acetate compound of the present invention is useful as a plasticizer for resins, particularly polyester resins. By adding a small amount of the benzyl diglycerin acetate compound of the present invention to the polyester resin, the crystallinity of the resin is suppressed to the extent that appropriate strength and heat resistance are maintained, and a flexible polyester resin composition is obtained. Since benzyl diglycerin acetate has a relatively high molecular weight, it is less volatile from the resin than conventional plasticizers such as diglycerin tetraacetate.

  Although it does not specifically limit as a polyester resin, The benzyl diglycerin acetate compound of this invention is suitable for the use to polylactic acid resin which is a biodegradable plastic, especially poly (L-lactic acid) (PLLA). . In particular, the benzyl diglycerin acetate compound of the present invention can be effectively used as a plasticizer in a polylactic acid resin composition in Japanese Patent Application No. 2006-146833, which is an application previously filed by the present inventors. The polylactic acid resin composition consists essentially of crystalline polylactic acid, noncrystalline polylactic acid and a plasticizer, and the noncrystalline polylactic acid is 5 to 5 of the total amount of crystalline polylactic acid and noncrystalline polylactic acid. It is a polylactic acid resin composition containing 33% by mass and a plasticizer in a proportion of 30% by mass or less of the total amount of the composition.

  The term “crystalline” in the term “crystalline polylactic acid” is used in the sense that a crystalline domain is observed with a polarizing microscope or the like after crystallization under moderate conditions. The crystalline polylactic acid is used in the meaning including a polymer of D-form lactic acid (hereinafter referred to as “poly-D-lactic acid”) or a polymer of L-form lactic acid (hereinafter referred to as “poly-L-lactic acid”). It may be a mixture of poly D lactic acid and poly L lactic acid (100/0 to 0/100: mass ratio). Poly-D lactic acid or poly-L lactic acid is a known compound, and as such, has essentially hard and brittle properties. In the present invention, as long as the definition of “crystallinity” is applied, in the case of poly-D lactic acid, an L-lactic acid monomer unit or a lactic acid monomer such as an aliphatic hydroxycarboxylic acid, an aliphatic diol, or an aliphatic dicarboxylic acid It may contain other monomer units that can be copolymerized. The same applies to poly L lactic acid. In the present invention, such a copolymer is also included in the crystalline polylactic acid.

The crystalline polylactic acid is not particularly limited as long as it has a molecular weight enough to dissolve in an appropriate solvent and remove the solvent from the solution to form a polylactic acid film. Such crystalline polylactic acid can be produced or available in a weight average molecular weight (Mw) range of 50,000 to 1,000,000, preferably 100,000 to 500,000, and is intended for use or molding. Depending on the product, crystalline polylactic acid is appropriately selected and selected. Commercially available products include Lacia H-100 (manufactured by Mitsui Chemicals), Toyota Eco Plastic U's (manufactured by Toyota Motor Corporation), and the like.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) used by this invention are using the standard polystyrene conversion value measured by the size exclusion chromatograph. The same applies hereinafter.

  The term “non-crystalline” in “non-crystalline polylactic acid” is used to mean that the crystal domain is not observed with a polarizing microscope or the like after crystallization under moderate conditions. Amorphous polylactic acid is used to mean a copolymer of D-form lactic acid and L-form lactic acid (hereinafter referred to as “poly-DL lactic acid”). The ratio of the D-form and the L-form may be any polymerization ratio as long as the above-mentioned non-crystallinity is ensured, and is appropriately selected and selected from the range of the D lactic acid: L lactic acid copolymer ratio 90:10 to 10:90. The The form of the copolymer may be any of a block copolymer, a graft copolymer, a random copolymer, and the like. In the present invention, as long as the definition of “non-crystalline” is applied, other monomer units copolymerizable with lactic acid monomers such as aliphatic hydroxycarboxylic acid, aliphatic diol, and aliphatic dicarboxylic acid may be included. . In the present invention, such a copolymer is also included in the amorphous polylactic acid.

  Amorphous polylactic acid can be produced or available in a weight average molecular weight (Mw) range of 50,000 to 1,000,000, preferably 100,000 to 500,000, and a commercially available product is Laissia H-280. (Mitsui Chemicals) is available.

  The amorphous polylactic acid is 50% by mass or less of the total amount of crystalline polylactic acid and amorphous polylactic acid, preferably 33% by mass or less, more preferably 30% by mass or less, and even more preferably at least 5% by mass or more. Try to use the amount. By adding non-crystalline polylactic acid to crystalline polylactic acid in this way, in combination with the addition of the plasticizer of the present invention, the crystallization progresses to such an extent that the practical strength and heat resistance are maintained. It is possible to suppress the decrease in flexibility and transparency over time. Even if the proportion of amorphous polylactic acid is too large, there is no further improvement in effect commensurate with the amount added, and there is a risk that strength and thermal resistance will be reduced and blocking will occur, and if it is too small, the above effect cannot be fully enjoyed. Occurs.

  When the plasticizer of the present invention is used in the polylactic acid resin composition as described above, the crystal size, crystal dispersibility, and crystallinity of crystalline polylactic acid can be controlled, resulting in strength and flexibility. Compatibility can be achieved and transparency can be ensured.

Materials used in the following examples: Poly (L-lactic acid) (PLLA) (H-100; manufactured by Mitsui Chemicals)
[Α] ²⁰ ₅₈₉ = −151 deg · dm ⁻¹ · g ⁻¹ · cm
Weight average molecular weight (Mw) = 156000,
Dispersion coefficient (M _w / M _n ) = 2.1

・ Diglycerin tetraacetate (DGTA) (PL-710: manufactured by Riken Vitamin Co., Ltd.)
Acetylated tributyl citrate (ATBC) (Citroflex A-4: manufactured by Morimura Corporation)

-Unless otherwise stated, materials (substances) available on the market were used. However, pyridine was distilled dried using CaH _2.

Measuring apparatus-Measurement of ¹ H-NMR spectrum: CD ₃ OD was used as a solvent, and JEOL LNM-GSX 400 (400 Hz) (manufactured by JEOL Ltd.) was used.

  Elemental analysis measurement: Perkin-Elmer 240C CHN-Corder (manufactured by Perkin Elmer) was used.

  Measurement of X-ray diffraction: Rigaku RINT InPlanc (manufactured by Rigaku Corporation) equipped with a CuKα source was used.

  Microscope observation: Polarized light microscope (BX 51; manufactured by Olympus)

-Tensile strength, elongation rate: A tensile testing machine (LUR-A-200NSA1; manufactured by Kyowa Denki Co., Ltd.) equipped with a 200N load cell was used.
Test piece: Gauge length 10 mm, at least 3 Crosshead speed: 1 mm / min

Measurement of TGA (thermogravimetric analysis): Measured with TG / DTA6200 (manufactured by SII).
Atmosphere: Air Temperature rising rate: 10 ° C / min

  Transparency measurement: Measure total light transmittance and HAZE according to JIS K 7136 with NDH2000 (Nippon Denshoku Industries Co., Ltd.).

[Synthesis of 1-O-benzyldiglycerin]
A solution of diglycerin (10 g, 60 mmol) in anhydrous DMF (40 mL) was added dropwise to sodium hydride (1.7 g, 72 mmol) under a nitrogen atmosphere. The mixture was stirred for 2 hours at room temperature. Benzyl chloride (7.6 g, 60 mmol) was added at room temperature. The temperature was then raised to 60 ° C. After stirring for 9 hours, the solvent was evaporated. The residue was extracted with n-butanol (160 mL) -water (160 mL × 2). The n-butanol layer was dried over MgSO ₄ , filtered and concentrated.

  The crude product was eluted with methanol / chloroform (1: 4) using silica gel column chromatography to give 3.0 g of 1-O-benzyldiglycerin (Rf = 0.57, 1: 9 methanol: chloroform). 17%).

^{The 1} H-NMR spectrum is shown in FIG.
¹ H-NMR (CD ₃ OD) δ 7.34-7.01 (m, 5H, aromatic proton), 4.63-4.35 (m, 2H, —O—CH ₂ —Ph), 3.87 -3.24 (m, 10H, methylene and methine protons).

Mass spectrometry MS (CI): m / z (intensity) = 257 (M ⁺ +1,100)

Infrared spectrum IR (cm ⁻¹ ): 3314 (wide), 2883, 2855, 1026

[Synthesis of 1-O-benzyldiglycerol triacetate]
Acetic anhydride (7.1 g, 70 mmol) was added to a solution of 1-O-benzyldiglycerin (2.5 g, 10 mmol) in pyridine (11 mL, 140 mmol) at 0 ° C. The reaction was performed at room temperature. After stirring for 18 hours, pyridine was removed.

The residue was extracted with diethyl ether (100 mL) and water (80 mL × 2). The diethyl ether layer was dried over MgSO ₄ , filtered and concentrated to obtain 2.17 g (57%) of 1-O-benzyl diglycerin triacetate.

^{The 1} H-NMR spectrum is shown in FIG.
¹ H-NMR (CD ₃ OD) δ 7.31-7.11 (m, 5H, aromatic proton), 5.12-5.00 (m, 2H, methylene proton), 4.61-4.32 ( _{m, 2H, -O-CH 2} -Ph), 4.30-3.39 (m, 8H, methylene protons), 1.99-1.85 (m, 9H, methyl protons)

Mass spectrometry MS (CI): m / z (intensity) = 233 (100), 383 (M ^{+ +1,} 17)

Elemental analysis C ₁₉ H ₂₆ O ₈ (382.40):
Calculated C 59.68, H 6.85,
Found C 59.41, H 6.61

Infrared spectrum IR (cm ⁻¹ ): 2836, 1732, 1215, 1038

  The TGA of 1-O-benzyl diglycerin triacetate (BGTA) is shown in FIG. It can be seen that the volatility is better than acetylated tributyl citrate (ATBC).

Synthesis of 1,1 ′, 2,2′-O-dibenzylidene diglycerol To a solution of diglycerol (8.3 g, 50 mmol) in DMF (100 mL), benzene (50 mL), benzaldehyde (53 g, 500 mmol) and p-toluene Sulfonic acid (5 mmol) was added. A Dean-Stark trap with a cooler was attached. The temperature was raised to 110 ° C. After stirring for 11 hours, the mixture was neutralized with Na ₂ CO ₃ (10 mmol). The solution was concentrated and extracted with water (80 mL) -dichloromethane (100 mL × 2). The dichloromethane layer was dried over MgSO ₄ , filtered and concentrated.

  The residue was purified using column chromatography with acetone / dichloromethane (1: 4) and 1,1 ′, 2,2′-O-dibenzylidene diglycerin (Rf = 0.87, 1: 9 methanol: Dichloromethane) 7.2 g (42%) was obtained.

^{The 1} H-NMR spectrum is shown in FIG.
¹ H-NMR (CD ₃ OD) δ 7.58-7.20 (m, 10H, aromatic proton), 5.95-5.67 (m, 2H, —O — (— O—) CH—Ph) , 4.48-3.42 (m, 10H, methylene and methine protons),

Mass spectrometry MS (CI): m / z (intensity) = 343 (M ⁺ +1,100)

Elemental analysis _{C 20 H 22 O 5 (342.39} ):
Calculated value C 70.16, H 6.48,
Found C 69.94, H 6.37

[Synthesis of 1,1′-O-dibenzyldiglycerin]
A solution of dibenzylideneglycerin (4.8 g, 14 mmol) in anhydrous diethyl ether (10 mL) was added dropwise to a 1 mol / L diisobutylaluminum hydride toluene solution (56 mL, 56 mmol) under a nitrogen atmosphere. The mixture was stirred for 18 hours at room temperature. Methanol and saturated NH ₄ Cl were added and stirred for 15 minutes. Thereafter, the solution was filtered to remove the solvent. Diethyl ether (25 mL) was added, insolubles were filtered off, and the ether layer was washed with water (50 mL × 2). The ether layer was dried over MgSO ₄ , filtered and concentrated.

  The residue was purified using silica gel column chromatography with acetone / dichloromethane (1: 4) and 1,1′-O-dibenzyldiglycerin (Rf = 0.87, 1: 9 methanol: dichloromethane). 4 g (7%) were obtained.

^{The 1} H-NMR spectrum is shown in FIG.
¹ H-NMR (CD ₃ OD) δ 7.45-7.07 (m, 10H, aromatic proton), 4.69-4.41 (m, 4H, —O—CH ₂ —Ph), 4.00 -3.39 (m, 10H, methylene and methine protons),

Mass spectrometry MS (CI): m / z (intensity) = 181 (100), 347 (M ⁺ +1,33)

Elemental analysis _{C 20 H 26 O 5 0.5H 2} O (355.47):
Calculated C 67.57, H 7.67,
Found C 67.9, H 7.39

Infrared spectrum IR (cm ⁻¹ ): 3431 (wide), 2882, 2858, 1736, 1231,
1024,735,697

[Synthesis of 1,1′-O-dibenzyldiglycerin diacetate]
Acetic anhydride (0.6 g, 6 mmol) was added at 0 ° C. to a solution of 1,1′-O-dibenzyldiglycerin (0.2 g, 0.6 mmol) in pyridine (5 mL, 60 mmol). After stirring for 18 hours at room temperature, pyridine was removed.

The residue was extracted with diethyl ether (30 mL) -water (50 mL × 2). The diethyl ether layer was dried over MgSO ₄ , filtered and concentrated to obtain 0.2 g (83%) of 1,1′-O-dibenzyldiglycerin diacetate.

^{The 1} H-NMR spectrum is shown in FIG.
¹ H-NMR (CD ₃ OD) δ 7.39-7.16 (m, 10H, aromatic proton), 5.21-4.95 (m, 2H, methine proton), 4.68-4.41 ( _{m, 4H, -O-CH 2} -Ph), 4.32-3.37 (m, 8H, methylene protons), 2.09-1.90 (m, 6H, methyl protons)

Mass spectrometry MS (CI): m / z (intensity) = 233 (100), 431 (M ⁺ +1, 2)

Elemental analysis _{C 24 H 30 O 7 (430.49} ):
Calculated C 66.96, H 7.02,
Found C 66.78, H 7.07

Infrared spectrum IR (cm ⁻¹ ): 2851, 1734, 1214, 1043, 697

  The TGA of 1,1'-O-dibenzyldiglycerin diacetate (DBGDA) is shown in FIG. It can be seen that the volatility is better than acetylated tributyl citrate (ATBC).

[Production of polylactic acid film]
PLLA is mixed with BGTA or DBGDA at a ratio of 100/0, 95/5, 90/10, 80/20, 70/30, 60/40, 50/50 (PLLA / BGTA or DBGDA) and casted. A polylactic acid film was prepared. PLLA, BGTA and DBGDA were dissolved in chloroform to a concentration of 1 g / dl before mixing. Each mixture (10 ml) was poured onto a Teflon plate (diameter 5 cm) and dried at room temperature for 48 hours.

  The tensile strength and elongation at break of the obtained film were measured. The results are shown in Table 1 below.

  The transparency of the obtained film was measured. Moreover, the bleeding out of the obtained film was observed. Bleed out was evaluated visually by observing the film surface visually with ◎ when no bleed out was observed, △ when slightly bleed out was observed, and × when bleed out was observed. The results are shown in Table 2. When the plasticizer of the present invention is used, transparency is maintained and bleed-out is small.

¹ H-NMR spectrum of 1-O-benzyl diglycerin. ¹ H-NMR spectrum of 1-O-benzyl diglycerin triacetate. 1,1 ', ¹ H-NMR spectrum of 2,2'-O-dibenzylidene ethylidenedioxy glycerin. ¹ H-NMR spectrum of 1,1′-O-dibenzyldiglycerin. ¹ H-NMR spectrum of 1,1′-O-dibenzyldiglycerin diacetate. TGA data for 1-O-benzyl diglycerin triacetate, 1,1'-O-dibenzyl diglycerin diacetate, acetylated tributyl citrate.

Claims (3)

Benzyldiglycerin acetate compound represented by the following chemical formula (I):

(In the formula, A represents CH ₃ CO—, or R ¹ C ₆ H ₄ CH ₂ — (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group);
B is R ² C ₆ H ₄ CH ₂ — (wherein R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyl group).   A polyester resin composition comprising polyester and benzyl diglycerin acetate represented by the chemical formula (I) according to claim 1. The composition according to claim 2, wherein the polyester is polylactic acid.

Images