JP3255200B2 - Polyester compound and organic gelling agent containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoreversible polyester type organic gelling agent having excellent hydrophilicity or lipophilicity. The gelling agent as referred to herein is a generic name of compounds having a function of giving a yield value to an applied system and eliminating the fluidity of the system.

[0002]

2. Description of the Related Art Hitherto, as organic thermoreversible low-molecular gelling agents, dibenzal sorbitol and substituted aromatic nuclei thereof, 12-hydroxystearic acid, acylated amino acid amides, cholesterol derivatives and the like have been known. It is used as a flow control agent and solid agent for paints and inks, a gel recovery agent for spilled oil, a solidifying agent for pesticides, an anti-slump agent for joints, a polymer processing aid, and a solidifying agent for fragrance. Have been.

[0003]

However, at present, the development of thermoreversible gelling agents is behind the development of thermoirreversible gelling agents by chemical crosslinking reactions.

[0004] In particular, cosmetics using glycerin, propylene glycol, ethylene glycol or the like as a hydrophilic base,
In the fields of excipients by forming gels of pharmaceuticals and marking materials or aqueous inks and aqueous paints, the development of gelling agents with improved hydrophilicity is expected. The same applies to the use of a printing plate material such as gel formation / ultraviolet curing of a hydrophilic acrylic resin. On the other hand, various gelling agents that can be used in the lipophilic molten polyethylene resin field, lipophilic inks, paints and the like are also desired.

Therefore, the development of a new thermoreversible gelling agent having new properties, especially excellent hydrophilicity or lipophilicity, contributes to the development of the thermoreversible gelling agent, which has been delayed in the conventional development. It provides a new and useful application to this product, and its industrial value is great.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a polyester having a specific structure functions as a thermoreversible gelling agent having excellent hydrophilicity or lipophilicity. And completed the present invention based on such knowledge. Incidentally, a gelling agent having a polyester structure, including the polyester according to the present invention, has not been known so far.

The organic gelling agent according to the present invention is characterized in that a polyester having a repeating unit represented by the general formula (1) is used as an active ingredient.

-OC-A-COO-BO- (1) wherein A is the following formula

[0009]

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Wherein t represents 1 or 0, and represents a 1,3: 2,4-dibenzylidene sorbitol residue or a 1,3: 2,4-dibenzylidene xylitol residue represented by the formula: B represents a residue formed by removing two hydroxyl groups (particularly, two terminal primary hydroxyl groups) from a polyhydric alcohol. That is, the polyester compound of the present invention contains A in the main chain, that is, the structure represented by the general formula (2). The structure represented by the general formula (2) is known as an organic gelling agent. The present inventor has discovered that the polyester compound having the skeleton A incorporated in the main chain has a function as a gelling agent regardless of the size and type of the terminal group. Therefore, the terminal group of the polyester represented by the formula (1) can be arbitrarily converted by a conventional method. For example, the terminal hydroxyl group can be changed to an acetyl group, a benzoate group, an alkyl ether (having 1 to 18 carbon atoms) or the like according to a conventional method. , Can be easily converted. The present invention has been completed based on this finding.

As used herein, the term "polyester" is intended to include diesters containing two ester groups in the molecule and polyesters containing more than two ester groups in the molecule.

In the polyester compound of the present invention, the number of repeating units of the formula (1) is not particularly limited as long as a predetermined effect can be obtained.
About 20 to 20 and preferably about 1 to 10 are recommended.

According to a preferred embodiment of the polyester of the present invention, the following general formulas (3), (4), (5) and (6)
And a compound represented by (7).

Formula (3) R ¹ OOC-A-COO-BOH (3) wherein A and B are the same as above. R ¹ represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. ]
A polyester compound represented by

General formula (4) HOBO- (OC-A-COO-BO) _p -H (4) wherein A and B are the same as above, and p is an integer of 1-20. ] The polyester compound represented by these.

Formula (5) R ² O- (OC-A-COO-BO) _m -CO-A-COOR ³ (5) wherein A and B are as defined above, and R ² and R ³ is the same or different and is an alkyl group, preferably having 1 to carbon atoms.
And 20 represents an alkyl group, and m is an integer of 1 to 20. ] The polyester compound represented by these.

General formula (6) HOBO- (OC-A-COO-BO) _n -CO-A-COOR ⁴ (6) wherein A and B are the same as above, R ⁴ is an alkyl group, It preferably represents an alkyl group having 1 to 20 carbon atoms, and n
Is an integer of 1 to 20. ] The polyester compound represented by these.

Among the compounds of the above general formula (4), the compounds of the following general formula (7) are easily produced.

[0019]

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Wherein A is the same as above,
q represents an integer of 1 to 13, and r represents an integer of 2 to 10. ]
A polyester compound represented by

The polyester according to the present invention can be produced relatively easily, for example, as follows. That is, the compounds of the general formulas (3) to (7) are converted to the compound of the general formula (8)

[0022]

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Wherein R ⁵ and R ⁶ are the same or different and each represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. t represents 1 or 0. 1,3:
2,4-bis (alkoxycarbonylbenzylidene) sorbitol, 1,3: 2,4-bis (alkoxycarbonylbenzylidene) xylitol, or a mixture thereof, and an excess amount of a polyhydric alcohol are mixed in the presence of a basic catalyst. Polycondensation at a temperature of about 20 ° C. to 200 ° C. for polyesterification, or polyhydric alcohol and an equimolar or excess amount of at least one compound of formula (8) in the presence of a basic catalyst It is obtained by polycondensing at a temperature of about 20 to 200 ° C. below to form a polyester. This reaction can be performed without a solvent or in the presence of a solvent.

The compound of the above general formula (8) used as a starting material in this reaction is described, for example, in EP507950.
As described in A1 publication, sorbitol or xylitol and formyl benzoic acid alkyl ester are
It is produced by heat condensation at about 20 to 200 ° C. in the presence of an acid catalyst in the presence of a solvent. As the alkyl formyl benzoate, a C ₁ -C ₂₀ alkyl ester of formyl benzoic acid, particularly methyl p-formyl benzoate, is preferred. In the synthesis reaction of the compound of the general formula (8), about 1-3 mol of alkyl formylbenzoate is used per 1 mol of sorbitol or xylitol. The reaction is carried out in water or by using an organic solvent inert to the reaction as a solvent, for example, a hydrocarbon having about 8 to 12 carbon atoms, cyclohexane, or a C ₁ -C ₃ alkyl-substituted cyclohexane. As the catalyst, sulfuric acid, paratoluenesulfonic acid and the like can be used. The reaction time is about 2 to 6 hours.

In the compound of the general formula (8) thus obtained, the substitution position of the ester group on the benzene nucleus may be any of the ortho, meta and para positions. As R ⁵ and R ⁶ , a methyl group, an ethyl group, a propyl group, a butyl group,
Examples thereof include alkyl groups such as an octyl group, a dodecyl group, and a stearyl group. Preferred examples of the compound of the general formula (8) include, for example, 1,3: 2,4-bis (methoxycarbonylbenzylidene) sorbitol, 1,3: 2,4-bis (methoxycarbonylbenzylidene) xylitol,
Alternatively, a mixture thereof can be exemplified. In the present invention, the compounds of the above general formula (8) may be used alone or in combination of two or more.

As the polyhydric alcohol, those corresponding to B in the above general formula (1) are used. Preferred polyhydric alcohols include ethylene glycol; diethylene glycol and other polyethylene glycol oligomers, especially polyethylene glycol having a degree of polymerization of about 2 to 1000 (preferably polyethylene glycol having a degree of polymerization of about 3 to 200); propylene glycol; dipropylene glycol and other polypropylene Glycol oligomers, especially polypropylene glycol having a degree of polymerization of about 2 to 1000 (preferably polypropylene glycol having a degree of polymerization of about 3 to 200); butanediol; pentanediol; hexamethylene glycol; xylylene glycol or its hydrogenated hydrogen and ethylene thereof Oxide adducts (number of moles of ethylene oxide added: about 1 to 50); bisphenol A and its nuclear hydrogenated product and their ethylene oxide Side adduct (ethylene oxide addition molar number: 1 to 50); glycerin, diglycerin,
Polyols such as triglycerin and other polyglycerin oligomers (preferably polyglycerin oligomers having a degree of polymerization of about 2 to 20), polyethylene having hydroxyl groups at both α and ω terminals (number average molecular weight Mn = 10000 or less, preferably 200 to 4000), polybutadiene having hydroxyl groups at both ends (number average molecular weight Mn = 1)
10,000 or less, preferably 200 to 4000), hydrogenated polybutadiene having hydroxyl groups at both ends (number average molecular weight Mn = 10,000 or less, preferably 200 to 4000), polyisoprene having hydroxyl groups at both ends (number average molecular weight Mn = 10,000 or less, preferably 200 to 4000),
Hydrogenated polyisoprene having hydroxyl groups at both ends (number average molecular weight Mn = 10000 or less, preferably 200 to 4
000). These can be used alone or in combination of two or more.

In particular, when producing the compound of the general formula (7), glycerin or polyglycerin oligomer represented by the following formula (9) is used as the polyol. The compound of the formula (9) is a known and easily available compound.

[0028]

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[In the formula, q represents an integer of 1 to 13. ]
When a linear polyester is produced by a polycondensation reaction using a polyhydric alcohol having two or more primary hydroxyl groups and one or more secondary hydroxyl groups, the primary hydroxyl group Is much larger than the secondary hydroxyl group, and usually, the primary hydroxyl group participates in the reaction, and the secondary hydroxyl group does not participate in the reaction. Therefore, the secondary hydroxyl group may not be protected. Therefore, for example, when the polyol of the above general formula (9) is used, it is usually effective to protect the secondary hydroxyl group without protecting the secondary hydroxyl group.
It can be treated as a secondary alcohol, that is, a telechelic alcohol, and can be subjected to the reaction as it is, and the polyester compound of the general formula (7) can be easily obtained.

In the polyesterification polycondensation reaction for forming the structure of the general formula (1), a predetermined amount is selected according to the monomer charging ratio of the compound of the general formula (8), which is a divalent carboxylic acid ester, and the polyhydric alcohol. Can be obtained in high yield.

That is, in the general formula (4), p becomes smaller as the proportion of the polyhydric alcohol used becomes larger than the equimolar charge, and the diester (p = 1), tetraester (p = 2) and the like become lower. The yield of the molecular weight polyester increases,
The molecular weight of the resulting polyester tends to decrease.

Conversely, as the charge ratio of the compound of the general formula (8) becomes larger than that of the equimolar charge, the product is converted from the mixture of the compounds of the general formulas (4), (5) and (6) by a general method. It changes to the polyester of the formula (5). In order to increase the molecular weight of the polyester, it is preferable to use a raw material having a high purity while bringing the charged monomer ratio close to the stoichiometric amount. The compound of the general formula (3) is prepared by stopping the reaction at an expected stage of the polycondensation reaction for producing the compound of the general formula (4) or (5), or by using a polyhydric alcohol having a large molecular weight as a monomer. Can be obtained relatively easily by transesterification with the compound of the general formula (8).

The molecular weight of the polyester compounds of the above general formulas (3) to (7) is generally determined by the degree of purification of the reaction raw materials and the solvent, the ratio of charged monomers between the polyhydric alcohol and the compound of the general formula (8) [more specifically, The ratio of the total number of moles of primary hydroxyl groups contained in the charged polyhydric alcohol to the total number of moles of ester groups contained in the charged compound of the general formula (8) (hereinafter simply referred to as “primary OH / And the reaction temperature, etc. That is, the higher the degree of purification of the reaction raw materials and the solvent, the closer the primary OH / ester group ratio is to 1, and the higher the reaction temperature. Well,
The molecular weight of the resulting polyester compound tends to increase.

On the other hand, whether the terminal group of the resulting polyester compound is a hydroxyl group or an alkyl group derived from an ester residue of the compound of the general formula (8) to be used,
Primarily due to the primary OH / ester group ratio. In general, if the primary OH / ester group ratio is much larger than 1, both end groups of the polyester compound formed at the end point of the reaction will be different from those of the compound of the formula (4), depending on the kind of raw material used. , Both tend to be hydroxyl groups.

If the primary OH / ester group ratio is slightly greater or slightly less than 1 or substantially equal to 1, the resulting polyester compound will be terminated at one end as in the compound of formula (6). In addition to a polyester compound having a hydroxyl group having an alkyl group at the other end, a compound having both hydroxyl groups such as a compound of the formula (4) or an alkyl group such as a compound of the formula (5) There is a tendency that certain compounds are mixed.

Further, when the primary OH / ester group ratio is much smaller than 1, the resulting polyester compound is
As in the compound of the formula (5), there is a tendency to have alkyl groups at both ends.

Accordingly, if the relationship between the primary OH / ester group ratio, the degree of purification of the raw materials and the reaction temperature, and the degree of polymerization or structure of the produced polyester is determined in advance, the desired polyester can be easily obtained. it can.

In general, the amount of the polyhydric alcohol to be used is appropriately selected depending on the structure of the target polyester, and is not particularly limited. When the polyester of the general formula (4) is produced, usually, the polyester of the general formula (8) It is recommended that the polyhydric alcohol be used in an amount of about 2 to 150 mol, preferably about 20 to 80 mol, per 1 mol of the monomer. If the polyhydric alcohol is used in excess, it also acts as a reaction solvent.

When the compound of the general formula (5) is produced, the monomer of the general formula (8) is used in an amount of about 2.0 to 20 mol, preferably about 3 to 10 mol, per mol of the polyhydric alcohol. It is recommended that

When the compound of the general formula (6) is produced, the monomer of the general formula (8) is used in an amount of about 0.2 to 2.0 mol, preferably 0.5 to 1. 8
It is recommended that they be used on a molar basis. However, when producing the polyester compound of the general formula (6), the general formula (4)
It is generally difficult to reduce the by-products of the compounds of (5) and (5) to zero.

Examples of the alkali catalyst include alkali metals such as lithium, sodium and potassium, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride, sodium methylate, sodium ethylate, and the like.
Metal alcoholates such as potassium tert-butylate; metal amides such as sodium amide and diisopropyllithium amide; and other neutral or alkaline catalysts used in the esterification reaction (for example, tilan alcoholate, aluminum hydroxide, tin oxide, etc.). For example, about 0.01 to 10 mol is usually used per 1 mol of the monomer of the general formula (8).

In this reaction, no solvent may be used, but a solvent is used if necessary. As the reaction solvent, the general formula (8)
Any solvent can be used as long as it dissolves the monomer and the polyhydric alcohol and does not adversely affect the reaction. Specific examples of such solvents include tetrahydrofuran, ethers such as dioxane, benzene, toluene,
hydrocarbon solvents such as n-hexane and cyclohexane, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Aprotic polar solvents such as mixtures thereof; Although the amount of use is not particularly limited, about 200 to 5000 parts by weight is preferably used with respect to 100 parts by weight of the monomer of the general formula (8).

The reaction temperature is about 0 to 200 ° C, preferably about 20 to 180 ° C. The reaction time is 1-20
It is about an hour, preferably about 3 to 10 hours. Also,
If necessary, the reaction may be carried out in an inert gas such as nitrogen gas.

The reaction mixture thus obtained is usually in a homogeneous liquid state under heating, but becomes a gel-like solid when cooled to room temperature. This is dispersed and neutralized in a suitable neutralizing agent solution, for example, a weakly acidic aqueous solution of acetic acid, an aqueous solution of phosphoric acid, or a solution of methanolic propionate. The obtained crude product is washed with water and dried to obtain a pure compound of the general formula (3), the general formula (4) [the general formula (7)], the general formula (5) or the general formula (6) Get.

If necessary, the obtained product is further purified and the individual compounds of the general formulas (3) to (7) are isolated by a conventional separation and purification method, for example, chromatography. Is also good. However, the individual compounds of the general formulas (3) to (7) exhibit a desired gelling effect either alone or in an arbitrary combination (a mixture of two or more). Thus, they need not be separated into individual compounds.

The thus obtained general formulas (3), (4),
The compound (5), (6) or (7) generally has a melting point of about 260 ° C. or less, and is useful as a gelling agent having good low-temperature melting property.

The polyester compound of the present invention is useful in the same applications as conventional gelling agents, for example, for controlling the flow or solidification of paints and inks, for recovering gels from spilled oil, and for preventing slumps in joints. It is also useful as a molecular processing aid and a solidifying agent for fragrances.

In the compounds of the present invention, compounds having a terminal long-chain alkyl group, compounds having a long-chain hydrocarbon group in the structure represented by B, or compounds having a polyoxypropylene repeating unit are generally lipophilic, Useful for gelling lipophilic substances. On the other hand, among the compounds of the present invention, those containing a large amount of hydroxyl groups or those having a polyoxyethylene repeating unit or glycerin or polyglycerin repeating unit are generally hydrophilic and are useful for gelling a hydrophilic substance.

In particular, the polyester according to the present invention was added to a hydrophilic substance such as glycerin, propylene glycol, ethylene glycol or the like, or added to a lipophilic ink, paint, molten resin or the like in a small amount and dissolved by heating. After that, it has a feature that the whole can be easily gelled by cooling.

The amount of the polyester of the present invention to be used with respect to the above-mentioned hydrophilic substance or lipophilic substance is not particularly limited as long as a predetermined effect is obtained, but is usually 20% by weight or less based on the hydrophilic substance or lipophilic substance. Is added in an amount of 15% by weight or less, particularly about 1 to 10% by weight.

The gel thus formed is a thermoreversible gel which turns into a sol by heating and turns into a gel by cooling. Further, the polyester of the present invention can be used in combination with a conventionally known thermoreversible gelling agent, if necessary.

The polyester of the present invention is useful not only as a gelling agent but also as a modifier for the antistatic, antifogging, antifouling, and printability of a polyolefin resin. It is also useful as a nucleating agent having a function of promoting crystallization and improving rigidity, such as a crystalline polymer such as polyethylene, polypropylene, polyethylene terephthalate, and polybutadiene resin. In addition, it is also useful as a plasticizer that improves moldability without substantially reducing various properties of these crystalline resin compositions.

[0053]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments. The gel formation was evaluated by the following method.

Gel formation evaluation method: 0.3 g of the polyester (mixture) of the present invention is added to 10 g of a test substance (glycerin or ethylene glycol) and mixed by heating to form a one-phase solution. Next, it is cooled with water and left at room temperature for 5 minutes. Next, a load of 80 g / cm ² is applied by a glass rod to determine whether or not the glass rod can enter.

Example 1 A 50 equipped with a thermometer, a stirrer and a decanter equipped with a cooling pipe was used.
1,3: 2,4-bis (p
-Methyloxycarbonylbenzylidene) sorbitol 9.5 g (0.02 mol), triglycerin 96 g
(0.4 mol) and 1.6 g of a 28% sodium methylate methanol solution were added, and the mixture was heated with stirring at an oil bath temperature of 160 ° C. for 8 hours. Then, after cooling to room temperature, the gel-like solid was dispersed in 1 liter of a weakly acidic aqueous solution of acetic acid and filtered. The obtained crude product was washed with water and dried at normal pressure and 90 ° C. for 6 hours to obtain 12 g of a white solid.

As a result of analysis by gel permeation chromatography (hereinafter referred to as “GPC”), tetraester (p = 2, B = triglycerin residue in the general formula (4), hereinafter referred to as “polyester (a)”) ) And a hexaester (in the general formula (4), p = 3, B =
A mixture of triglycerin residues (hereinafter, referred to as “polyester (b)”) (weight ratio: (a) / (b) = 6/1).

The FT-IR spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3300, 292
8, 1718, 1614, 1578, 1285, 115
5,1090,850,750 cm ^-1 Melting point (° C): 140 to 165 Using the above mixture, gel formation was evaluated. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 2 Example 1 except that the oil bath temperature was changed to 200 ° C. instead of 160 ° C.
The same operation as described above was performed to obtain 10 g of a white solid. As a result of GPC analysis, the obtained product was a mixture of polyester (a) and polyester (b) (weight ratio: (a) / (b) = 1).
/ 8). FT-IR of the compound obtained below
3 shows spectral data.

FT-IR (KBr): 3295,293
0, 1725, 1615, 1580, 1280, 116
0,1085, 854, 745 cm ^-1 Melting point (° C): 130-150 This mixture was used to evaluate gel formation. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 3 Diethylene glycol 4 was used instead of 96 g of triglycerin.
Except that the amount was changed to 2.2 g (0.4 mol), the same procedure as in Example 1 was carried out to obtain 9.8 g of a white solid. As a result of GPC analysis, tetraester (B = diethylene glycol residue in general formula (4), p = 2, hereinafter referred to as “polyester (c)”), hexaester (B = B in general formula (4))
Diethylene glycol residue, p = 3, hereinafter referred to as “polyester (d)” and octaester (general formula (4)
Wherein B = diethylene glycol residue, p = 4, hereinafter referred to as “polyester (e)” (weight ratio:
(C) / (d) / (e) = 2/1/1). The spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3258,287
8, 1724, 1615, 1580, 1514, 128
3,1168,1095,857,752,710cm
^-1 Melting point (° C): 150 to 170 Using this mixture, gel formation was evaluated. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 4 10.5 g of a white solid was obtained in the same manner as in Example 1 except that 47.2 g (0.4 mol) of 1,6-hexanediol was used instead of 96 g of triglycerin. As a result of GPC analysis, tetraester (in the general formula (4), p = 2,
B = 1,6-hexanediol residue, hereinafter referred to as “polyester (f)”, hexaester (in the general formula (4), p = 3, B = 1,6-hexanediol residue,
Hereinafter, a mixture of polyester (g) and octaester (p = 4, B = 1,6-hexanediol residue in the general formula (4), hereinafter referred to as “polyester (h)”) (weight ratio: (F) / (g) / (h) = 1 /
2/1). The spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3243,287
6,1723,1615,1580,1279,109
8,854,751 cm ⁻¹ melting point (° C.): 130-145 Using this mixture, gel formation was evaluated. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 5 A white solid (11.4 g) was obtained in the same manner as in Example 1, except that 53.6 g (0.4 mol) of dipropylene glycol was used instead of 96 g of triglycerin. As a result of GPC analysis,
Tetraester (in the general formula (4), p = 2, B =
A mixture of a dipropylene glycol residue (hereinafter, referred to as “polyester (i)”) and a hexaester (in the general formula (4), p = 3, B = dipropylene glycol residue, hereinafter, referred to as “polyester (j)”) ( Weight ratio:
(I) / (j) = 4/1). The spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3270,287
7, 1718, 1616, 1579, 1278, 109
4,1020,831,750 cm ^-1 melting point (° C): 130-140 This mixture was used to evaluate gel formation. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 6 The procedure of Example 1 was repeated, except that 93 g of deglycerin (average degree of polymerization: 10) was used instead of 93 g of triglycerin, to obtain 30 g of a white solid. As a result of GPC analysis, the obtained product was represented by the following general formula (4): average polymerization degree p = 16,
B = Polyester with decaglycerin residue.

The spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3250,297
8, 1725, 1615, 1580, 1276, 109
4,1020,857,752 cm ^-1 melting point (° C): 50-60 This mixture was used to evaluate gel formation. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 7 4 g of 1,3: 2,4-bis (p-methyloxycarbonylbenzylidene) sorbitol was added to the same apparatus as in Example 1.
(0.084 mol), polyethylene glycol # 400
0 (average molecular weight 2879, MW / MN = 1.02) 25
g, potassium carbonate 7 g and dimethyl sulfoxide 100 m
and stirred under heating at 140 ° C. for 8 hours. After cooling to room temperature, potassium carbonate was filtered. Next, the filtrate was re-precipitated in 500 ml of isopropanol, and the precipitate was filtered and dried to obtain 20 g of a white solid.

As a result of GPC analysis, a monoester exchanger represented by the general formula (3) (MW3284, MW / MN =
1.04, R ¹ = methyl).

FT-IR (KBr): 2882, 171
8,1599,1558,1280,1242,111
4,964,844 cm ⁻¹ melting point (° C.): 50-68 Using this mixture, gel formation was evaluated. As a result, no glass rod penetrated into each test object, and gel formation with a gel strength of 80 g / cm ² or more was observed.

Example 8 A 50 equipped with a thermometer, a stirrer and a decanter equipped with a cooling pipe was used.
1,3: 2,4-bis (p
-Methoxycarbonylbenzylidene) sorbitol9.
5 g (0.02 mol), 55 g (0.6 mol) of glycerin and 1.6 g of a 28% methanol solution of sodium methylate were added, and the mixture was heated and stirred at an oil bath temperature of 160 ° C. for 8 hours.

After cooling to room temperature, the gel-like solid was dispersed in 1 liter of a weakly acidic aqueous solution of acetic acid and filtered. The obtained crude product was washed with water and dried at normal pressure and 90 ° C. for 6 hours to obtain 12 g of a white solid. As a result of analysis by gel permeation chromatography, the main product was represented by the general formula (7)
Polyesters having q = 1 and r = 2 to 3 (theoretical molecular weight: 1096 (q = 1, r = 2), 1598 (q = 1, r
= 3)). The GPC chart is shown in FIG.

The GPC analysis was performed under the following conditions. still,
The molecular weight calibration curve was prepared using polyethylene glycol for preparing a GPC calibration curve.

Column: Shodex GPC KD80
3 + 802 Mobile phase: DMF Flow rate: 1 ml / min Pressure: 54 kg / cm ² Detector: RI temperature: 40 ° C. Spectral data of the compound obtained below.

FT-IR (KBr): 3285,293
8, 1723, 1615, 1580, 1283, 116
7,1095,856,752,711 cm ^-1 melting point (C): 220-240.

Example 9 13 g of a white solid was obtained in the same manner as in Example 8, except that 100 g (0.6 mol) of diglycerin was used instead of 55 g (0.6 mol) of glycerin. As a result of GPC analysis, the main product was a polyester of the general formula (7) with q = 2 and r = 2 to 3 (theoretical molecular weight 1318 (q = 2, r = 2), 18
94 (q = 2, r = 3). The GPC chart is shown in FIG.

The FT-IR spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3304, 293
2,1724,1615,1582,1282,116
5,1096,856,752 cm ^-1 melting point (C): 180-220.

Example 10 12.6 g of a white solid was obtained in the same manner as in Example 8, except that 144 g (0.6 mol) of triglycerin was used instead of 55 g (0.6 mol) of glycerin. As a result of GPC analysis,
A GPC chart having the same pattern as in Example 8 was obtained, and the main product was q = 3, r =
It was confirmed that it was 5-7 polyester.

The FT-IR spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3298,293
0, 1720, 1615, 1580, 1280, 116
0,1095, 854, 750 cm ^-1 melting point (C): 140-160.

Example 11 The procedure of Example 8 was repeated, except that 277 g (0.6 mol) of hexaglycerin (average degree of polymerization (q) = 6) was used instead of 55 g (0.6 mol) of glycerin. The obtained gel-like solid was dispersed in 1 liter of acetone, and 14 g of a white syrup-like substance was obtained by decantation. As a result of GPC analysis, a GPC chart having a pattern similar to that of Example 8 was obtained, and the main product was q in General Formula (7).
= 6, r = 5-7.

The FT-IR spectrum data of the obtained compound is shown below.

FT-IR (KBr): 3295,292
8, 1718, 1614, 1580, 1278, 116
5,1094,855,750 cm ^-1 .

Application Example 1 Each of the compounds of the present invention obtained in Examples 8 to 11 was 0.7
g was added to 50 g of each of ethylene glycol, glycerin and ethylene glycol at 130 ° C., and the mixture was heated and stirred for 5 minutes, and then cooled to room temperature. As a result, any compound was found to have a gel-forming ability.

Example 12 A 1000 ml separable flask is charged with 500 ml of N-methyl-2-pyrrolidone. R = RC of C ₁₈ alkyl
210.0 g (0.2 mol) and 12.4 g of bis (octadecyloxycarbonylbenzylidene) sorbitol and ethylene glycol, which are BSs, respectively.
(0.2 mol) The temperature was increased to 100 ° C. Next, 2.1 g of sodium methylate is added and stirred for 8 hours.
After the same neutralization and drying as in Example 1, 215 g of a white solid sample was obtained.

As a result of the GPC analysis, in equation (4), B =
An ethylene glycol residue, a compound having p = 1 to 3, a compound having R ² ＲR ³ = octadecyl, B = ethylene glycol residue, m = 1 to 3 in the formula (5), and a compound of the formula (6) in was a mixture of R ⁴ = octadecyl, B = ethylene glycol residues, the compounds are n = 1 to 3. (Weight ratio compound (4): compound (5): compound (6) = 1: 1: 2).

Melting point (° C.): 130-135. The evaluation result of the gel forming ability showed a gel strength of 80 g / cm ² or more.

[Brief description of the drawings]

FIG. 1 shows the GP of the polyester compound obtained in Example 8.
It is a C chart.

FIG. 2 shows the GP of the polyester compound obtained in Example 9.
It is a C chart.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (12)

(57) [Claims] 1. General formula (1) -OC-A-COO-BO- (1) wherein A is the following formula: (Where t represents 1 or 0) 1,3:
2,4-dibenzylidene sorbitol residue or 1,
3: indicates a 2,4-dibenzylidene xylitol residue;
B represents a residue formed by removing two hydroxyl groups from a polyhydric alcohol. ] The polyester compound which has a repeating unit represented by these. 2. Formula (3) R ¹ OOC-A-COO-BOH (3) wherein A and B are the same as above, and R ¹ represents an alkyl group. ] The polyester compound of Claim 1 represented by these. 3. General formula (4) HOBO- (OC-A-COO-BO) _p -H (4) wherein A and B are the same as those in claim 1,
Is an integer of 1 to 20. ] The polyester compound of Claim 1 represented by these. 4. General formula (5) R ² —O— (OC—A—COO—BO) _m —CO—A—COOR ³ (5) wherein A and B are the same as defined in claim 1. Yes, R
² and R ³ are the same or different and each represent an alkyl group;
Is an integer of 1 to 20. ] The polyester compound of Claim 1 represented by these. 5. General formula (6) HOBO- (OC-A-COO-BO) _n -CO-A-COOR ⁴ (6) wherein A and B are the same as those in claim 1,
⁴ represents an alkyl group, and n is an integer of 1 to 20. ]
The polyester compound according to claim 1, which is represented by the formula: 6. A compound of the general formula (7) [Wherein, A is the same as in claim 1, and q is 1 to
13 represents an integer, and r represents an integer of 2 to 10. ] The polyester compound of Claim 1 represented by these. 7. A general formula (1): -OC-A-COO-BO- (1) wherein A is a compound represented by the following formula: (Where t represents 1 or 0) 1,3:
2,4-dibenzylidene sorbitol residue or 1,
3: indicates a 2,4-dibenzylidene xylitol residue;
B represents a residue formed by removing two hydroxyl groups from a polyhydric alcohol. ] An organic gelling agent comprising a polyester compound having a repeating unit represented by the formula: 8. A polyester compound represented by the general formula (3): R ¹ OOC-A-COO-BOH (3) wherein A and B are the same as those in claim 7;
¹ represents an alkyl group. The organic gelling agent according to claim 7, which is a compound represented by the formula: 9. A polyester compound represented by the general formula (4): HOBO- (OC-A-COO-BO) _p -H (4) wherein A and B are the same as those in claim 7;
Is an integer of 1 to 20. The organic gelling agent according to claim 7, which is a compound represented by the formula: 10. A polyester compound represented by the following general formula (5): R ² -O- (OC-A-COO-BO) _m -CO-A-COOR ³ (5) The same as in
² and R ³ are the same or different and each represents an alkyl group;
m is an integer of 1 to 20. The organic gelling agent according to claim 7, which is a compound represented by the formula: 11. A polyester compound represented by the general formula (6): HOBO- (OC-A-COO-BO) _n -CO-A-COOR ⁴ (6) wherein A and B are the same as defined in claim 7. And R
⁴ represents an alkyl group, and n is an integer of 1 to 20. ]
The organic gelling agent according to claim 7, which is a compound represented by the formula: 12. The polyester compound represented by the general formula (7): [Wherein, A is the same as in claim 7, and q is 1 to
13 represents an integer, and r represents an integer of 2 to 10. The organic gelling agent according to claim 7, which is a compound represented by the formula: