JP2005089305A - New rosin compound, method for producing the same and surfactant or additive for resin comprising the same rosin compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new rosin compound having a rosin skeleton and a plurality of hydroxy groups in one molecule and exhibiting high surface-activity and to further provide a method for production by which the new rosin compound can selectively be produced in high yield. <P>SOLUTION: The rosin compound is obtained by reacting a rosin glycidyl ester (A) with a polyol (B) having ≥3 hydroxy groups and has the ≥3 hydroxy groups. The method for producing the rosin compound and a surfactant comprising the rosin compound are provided. An additive for a resin comprises the rosin compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel rosin compound having a hydrophobic rosin skeleton residue and a plurality of hydrophilic hydroxyl groups, and a selective synthesis method thereof. The present invention also relates to a surfactant and a resin additive containing the rosin compound.

   The surfactant is composed of a compound having a hydrophobic part and a hydrophilic part in one molecule. Therefore, if it is possible to produce a compound having a lot of hydroxyl groups with high hydrophilicity and a rosin skeleton with high hydrophobicity in one molecule, it is possible to obtain a surfactant having excellent surface activity and natural. Since rosins derived from products are used as raw materials, it is considered that the burden on the environment can also be reduced. Moreover, it is thought that such a compound can be used as an additive for a resin such as a compatibilizing agent by adding it to various resins such as a plastic because of the structure of the compound. As such a compound, for example, a compound in which a part of hydroxyl groups of a polyol is esterified with a rosin is considered preferable. To produce the compound, a part of the polyol is selectively used. It is necessary to esterify.

  As a method for producing such a compound, for example, an esterification reaction between rosins and polyglycerin has been proposed (see Patent Document 1). However, in the production method, a carboxyl group of rosins and polyglycerin and the like are proposed. The hydroxyl groups such as polyglycerin in the reaction product were almost all esterified because they were reacted at a charging ratio such that the hydroxyl groups in the reaction mixture had the same amount.

A method of reducing the charge ratio of rosins / polyols to produce a reaction product having a large hydroxyl value is also conceivable. A mixture with the polyol of the reaction is obtained, and a reaction product obtained by selectively esterifying a part of the hydroxyl groups of the polyol cannot be obtained. The reason for this is that, in the initial stage of the reaction, only one hydroxyl group of the polyol is esterified with rosins, and the hydrophobicity of the esterified polyols increases, so that High compatibility and poor compatibility with highly hydrophilic polyols, resulting in preferential esterification of rosins with already partially esterified polyols rather than unreacted polyols This is thought to be due to a reaction. Moreover, since the carboxyl group of rosins is a tertiary carboxyl group and has a large steric hindrance, it is usually necessary to heat to about 280 ° C. during esterification. In addition to being easy to proceed, at such a high temperature, a transesterification reaction occurs between the esterified polyols once formed, and as a result, more esterified polyols and the starting polyol One of the reasons is considered to be generated.

US Pat. No. 1,696,337

  In light of the above problems, the present invention provides a novel rosin compound having a rosin skeleton and a plurality of hydroxyl groups in one molecule and capable of expressing high surface activity, and further, selectively and highly enhances the novel rosin compound. It aims at providing the manufacturing method which can be manufactured with a yield.

  In order to achieve this object, the present inventor has intensively studied and found that a novel rosin compound having a number of hydroxyl groups in the molecule can be provided by reacting rosin glycidyl ester with polyols.

  That is, the present invention relates to a rosin compound having three or more hydroxyl groups obtained by reacting rosin glycidyl ester (A) with a polyol (B) having three or more hydroxyl groups; rosin glycidyl ester (A) and 3 hydroxyl groups. A method for producing a rosin compound having three or more hydroxyl groups, which is reacted with at least one polyol (B); a surfactant characterized by containing the rosin compound; It relates to additives for resins.

  According to the present invention, a novel rosin compound having a rosin skeleton and a plurality (at least three or more) of hydroxyl groups in one molecule can be provided. Further, according to the production method of the present invention, a rosin ester can be produced in a selective and high yield partly of a polyol quickly at a relatively low temperature. The novel rosin compound obtained in the present invention has a high surface activity.

  Examples of the rosin glycidyl ester (A) (hereinafter referred to as component (A)) used in the present invention include known rosin and its derivatives (hereinafter referred to as rosins) glycidyl ester. Specifically, gum rosin glycidyl ester, wood rosin glycidyl ester, tall oil rosin glycidyl ester, disproportionated rosin glycidyl ester, hydrogenated rosin glycidyl ester, dehydrogenated rosin glycidyl ester, maleated rosin glycidyl ester, fumarated rosin Examples thereof include glycidyl ester and acrylated rosin glycidyl ester. In addition, as glycidyl esters of resin acids obtained by purifying these rosins, abietic acid glycidyl ester, levopimaric acid glycidyl ester, neoabietic acid glycidyl ester, pastrinic acid glycidyl ester, pimaric acid glycidyl ester, isopimaric acid glycidyl ester, sandaracopimalic acid Glycidyl ester, dehydroabietic acid glycidyl ester, dihydroabietic acid glycidyl ester, tetrahydroabietic acid glycidyl ester, maleopimalic acid triglycidyl ester, fumaropimaric acid triglycidyl ester, acrylopimaric acid diglycidyl ester, and the like can also be used. The component (A) is usually obtained by reacting rosins and the like with epichlorohydrin and the like. As the production method, for example, methods described in JP-A-1-069680, JP-A-59-039885 and JP-A-59-039886 can be employed.

  Moreover, it does not specifically limit as polyol (B) (henceforth (B) component) which has three or more hydroxyl groups used by this invention, Various well-known things can be used. Specifically, for example, polyglycerins such as diglycerin, triglycerin, tetraglycerin, glycerin, pentaerythritol, dipentaerythritol, erythritol, trimethylolethane, trimethylolpropane, pentatriol, sorbitol, sorbitan, mannitol, etc. Can be mentioned. Any of these polyols may be used alone or in combination of two or more. Among these, in particular, when glycerin or polyglycerins are used, a reaction product having a high surface activity is obtained. Therefore, these polyols are preferable when attention is paid to the surface active effect.

 The amount of component (A) and component (B) used in the present invention is appropriately determined in consideration of the molecular weight of component (B) and the epoxy equivalent of component (A) to be used. The epoxy equivalent of component (A) corresponds to the molecular weight of component (A) per epoxy group. In addition, when (B) component is a mixture which consists of several components, such as polyglycerol, (number average) molecular weight is determined by calculating from the hydroxyl value and theoretical hydroxyl value of (B) component. The The ratio of the number of moles of the component (B) to the number of moles of the component (A) based on the epoxy equivalent of the component (A) can be selected and determined as appropriate, but when considering the surface active effect, {(B ) Number of moles of component} / {number of moles of component (A) based on epoxy equivalent of component (A)} is usually about 1.0 to 5.0, preferably 1.0 to 3 .0. If it is less than 1.0, the unreacted component (B) remains, and the yield tends to decrease. If it exceeds 5.0, the hydrophilicity of the obtained rosin compound is reduced, and the surface active effect is obtained. Is often small.

  A rosin compound having a desired molecular weight and hydroxyl value can be produced by appropriately selecting and reacting the types and use ratios of the component (A) and the component (B). The reaction between the component (A) and the component (B) is an addition reaction in which the epoxy group of the component (A) reacts with the hydroxyl group of the component (B), and the epoxy ring is opened by adding the hydroxyl group to the epoxy group. To form a new hydroxyl group.

In the reaction of the component (A) and the component (B), it is not necessary to use a reaction catalyst, but there is an advantage that the reaction time can be shortened by using the reaction catalyst. As the reaction catalyst, general inorganic acids, organic acids and the like can be used. Examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Examples of the organic acids include methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, and the like. In consideration of dissolution in the component (A) and the component (B), it is particularly preferable to use sulfuric acid, methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid and the like. The amount of these catalysts used is usually about 0.0001% to 10% by weight, preferably 0.01% to 1% by weight, based on the weight of component (A). If it is less than 0.0001% by weight, the reaction time may be long, and even if it exceeds 10% by weight, there is no particular advantage.

  In the reaction of component (A) and component (B), the reaction proceeds without using a solvent, but various known solvents can be used as necessary. As the solvent, any solvent that does not react with an epoxy group or a hydroxyl group can be used freely. Specifically, ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ketone solvents such as MEK and MIBK, DMF, and the like. , DMSO, sulfolane and the like. The solvent used preferably has a boiling point of 80 ° C. or higher. When the boiling point is less than 80 ° C., depending on the reaction temperature, it may be disadvantageous because it is a pressurized reaction.

  Although the reaction temperature of (A) component and (B) component in this invention is not specifically limited, About 60 to 250 degreeC is preferable, Especially preferably, it is 80 to 180 degreeC. When reaction temperature is less than 60 degreeC, reaction may become difficult to advance, and when it exceeds 250 degreeC, there is no advantage in particular. In addition, when using a reaction catalyst, reaction can be advanced at low temperature.

  In the present invention, the reaction time between the component (A) and the component (B) depends on the reaction temperature, but is usually about 1 to 48 hours. In order to determine the end of the reaction, gas chromatography, gel permeation chromatography, liquid chromatography or the like may be used, and the reaction may be terminated when the peak of rosin glycidyl ester disappears.

In addition, although (B) component may contain water, in that case, since water may react with the epoxy group of (A) component, (B) component is used. It is preferable to perform a dehydration operation before. As the dehydration method, a known method can be used. For example, a method in which the component (B) is put in a reactor before the reaction is performed, and the water is evaporated and removed under reduced pressure can be employed. Depending on the heating temperature, the components (A) and (B) may be placed in the reactor, and water may be removed by evaporation while reducing the pressure.

  The rosin compound thus obtained is one in which at least one hydroxyl group of the component (B) is reacted with the epoxy ring of the component (A) and has at least three or more hydroxyl groups in one molecule. . For example, when the rosin compound is reacted using glycidyl ether of dehydroabietic acid as the component (A) and glycerin as the component (B), the general formula (1):

In the case where glycidyl ether of dehydroabietic acid is used as the component (A) and polyglycerin is used as the component (B), the general formula (2):

(Where n is an integer of 2 or more). The target rosin compound usually has a yellow appearance and is a viscous liquid at room temperature. The hydroxyl value of the rosin compound varies depending on the component (B) used, but is usually about 150 to 600.

Since the rosin compound has high surface activity, it can be used as a surfactant. When used as a surfactant, the hydroxyl value is usually preferably about 400 to 600.

The rosin compound can also be used as an additive for resins. When used as an additive for resins, it is preferable to appropriately control the hydroxyl value and the like according to the resin used.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Example 1
In a reaction vessel equipped with a stirrer, thermometer, decompressor and condenser, 35.6 g (0.1 mol) of glycidyl dehydroabietic acid and 9.2 g (0.1 mol) of glycerin and paratoluenesulfonic acid / water 35.6 mg of the Japanese product was charged and reacted at 150 ° C. and 5 KPa for 6 hours to obtain 44.7 g of a slightly yellow viscous liquid. As a result of analyzing the reaction product by gel permeation chromatography, dehydroabietic acid glycidyl ester disappeared and the hydroxyl value was 405.

The reaction product is obtained from Thermo Nicolet, AVATOR360.
It measured by ATR method with the FT-IR spectrometer. The results were as follows.
IR: 3600-3200 cm ⁻¹ , 1723 cm ⁻¹ , 1711 cm ⁻¹ , 1245 cm ⁻¹ , 1124 cm ⁻¹ , 1109 cm ⁻¹ , 1039 cm ⁻¹
Further, 10 g of the reaction product was dissolved in 100 g of toluene, and 10.2 g (0.1 mol) of acetic anhydride and 10.1 g (0.1 mol) of triethylamine were added and stirred at room temperature for 18 hours. After stirring, 5 g of ethanol and 200 g of water were added and stirred for 1 hour, and then the organic layer and the aqueous phase were separated with a separatory funnel. The organic layer was washed 3 times with 200 g of water and then dried over anhydrous sodium sulfate. Toluene was distilled off to obtain 12.2 g of acetylated product. 4 g of the obtained acetylated product was collected and separated by silica gel column chromatography. (Silica gel amount is 300 g, solvent is hexane / ethyl acetate = elution by gradually changing the composition from 90/10 to 70/30)
The solvent was distilled off from the separated elution fraction to obtain 2.95 g of a slightly yellow viscous liquid. This was analyzed by NMR. NMR was ATR-300 manufactured by Bruker. The results were as follows.
¹ H-NMR (δ, CDCl ₃ ): 7.16 (1H, d), 6.97 (1H, d), 6.87 (1H, d), 5.1-5.3 (2H, m) 4.29 (2H, m), 4.13 (2H, m), 3.5-3.7 (4H, m), 2.86 (2H, m), 2.81 (1H, m), 2 .23 (1H, d), 2.21 (1H, m) 2.05 (9H, s), 1.4-2.0 (7H, m) 1.27 (3H, S) 1.22 (6H D), 1.21 (3H, s)

From the IR results, it is clear that the slightly yellow viscous liquid has a hydroxyl group, and from the NMR results, this liquid has the general formula (1):

(In the formula, Ac represents an acetyl group)
It is estimated that it is a compound represented by. That is, the structure before acetylation has the general formula (2):

It is estimated that it is a compound represented by. This is a reaction product of rosin glycidyl ester and glycerin.

Example 2
In a reaction vessel equipped with a stirrer, a thermometer, a decompression device and a cooling tube, 42.3 g of disproportionated rosin glycidyl ester (Arakawa Chemical Industries, KE-309, epoxy equivalent 423) and 9.2 g of glycerin (0. 1 mol) and 42.3 mg of paratoluenesulfonic acid monohydrate were added and reacted at 150 ° C. and 5 KPa for 6 hours to obtain 51.1 g of a yellow viscous liquid. As a result of analyzing the reaction product by gel permeation chromatography, rosin glycidyl ester disappeared and the hydroxyl value was 360.
^{IR: 3600-3200cm -1, 1722cm -1,} 1709cm -1, 1244cm -1, 1124cm -1, 1111cm -1, 1040cm -1

Example 3
The same procedure as in Example 2 was repeated, except that diglycerin (Sakamoto Yakuhin Kogyo Co., Ltd., Diglycerin S) 16 and 6 g (0.1 mol) was used. 57.9 g of liquid was obtained.
^{IR: 3600-3200cm -1, 1723cm -1,} 1712cm -1, 1245cm -1, 1124cm -1, 1110cm -1, 1040cm -1

Example 4
Disproportionated rosin glycidyl ester (Arakawa Chemical Industries, Ltd., KE-309, epoxy equivalent 423) 42.3 g and polyglycerin (Sakamoto Pharmaceutical Co., Ltd. stock) in a reaction vessel equipped with a stirrer, thermometer, decompressor and condenser. 38.7 g (manufactured by company, polyglycerin # 500, hydroxyl value 962, containing 10.1% by weight of water) was added and dehydrated at 100 ° C. and 5 KPa. To this, 42.3 mg of paratoluenesulfonic acid monohydrate was added and reacted at 150 ° C. for 8 hours to obtain 76.0 g of a yellow viscous liquid. As a result of analyzing the reaction product by gel permeation chromatography, rosin glycidyl ester disappeared and the hydroxyl value was 452.
IR: 3600-3200 cm ⁻¹ , 1724 cm ⁻¹ , 1710 cm ⁻¹ , 1245 cm ⁻¹ , 1125 cm ⁻¹ , 1109 cm ⁻¹ , 1038 cm ⁻¹

Example 5
The same procedure was performed except that the amount of polyglycerin charged in Example 4 was changed to 19.4 g, to obtain 59.6 g of a yellow viscous liquid having a hydroxyl value of 298.
^{IR: 3600-3200cm -1, 1722cm -1,} 1709cm -1, 1245cm -1, 1125cm -1, 1110cm -1, 1039cm -1

Example 6
The polyglycerol of Example 4 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 500, hydroxyl value 962, containing 10.1% by weight of water) was changed to 38.7 g. (Hydroxyl value 885, containing 10.1% by weight of water) The same operation was performed except that the content was changed to 42.0 g, to obtain 79.3 g of a yellow viscous liquid having a hydroxyl value of 440.
IR: 3600-3200 cm ⁻¹ , 1723 cm ⁻¹ , 1711 cm ⁻¹ , 1246 cm ⁻¹ , 1124 cm ⁻¹ , 1112 cm ⁻¹ , 1042 cm ⁻¹

Example 7
The same procedure was performed except that the amount of polyglycerin charged in Example 6 was changed to 21.0 g, to obtain 60.8 g of a yellow viscous liquid having a hydroxyl value of 295.
^{IR: 3600-3200cm -1, 1722cm -1,} 1711cm -1, 1245cm -1, 1124cm -1, 1109cm -1, 1038cm -1

Evaluation Example 1
When 1 g of the rosin compound obtained in Examples 4 and 6 was added to 99 g of water and stirred, it was dispersed in a micelle form.

The novel rosin compound of the present invention can be used as a nonionic surfactant. In particular, the surfactant can be suitably used as a surfactant for foods, papermaking emulsion sizes, adhesive emulsions and the like. Further, the novel rosin compound of the present invention is used as a modifier for plastics, rubber, etc., specifically as an antifogging agent for plastic films, an antistatic agent, a compatibilizer for polymer alloys, a modifier for coating materials, etc. Widely applicable.

Claims (6)

A rosin compound having three or more hydroxyl groups obtained by reacting rosin glycidyl ester (A) with a polyol (B) having three or more hydroxyl groups. The rosin compound according to claim 1, wherein the polyol (B) having three or more hydroxyl groups is at least one selected from the group consisting of glycerin and polyglycerin. A method for producing a rosin compound having three or more hydroxyl groups, comprising reacting rosin glycidyl ester (A) with a polyol (B) having three or more hydroxyl groups. The method for producing a rosin compound according to claim 3, wherein the reaction is carried out in the presence of an acid catalyst. A surfactant comprising the rosin compound according to claim 1. A resin additive comprising the rosin compound according to claim 1.