JP6147410B2 - Method for producing sucrose carboxylate - Google Patents

Description

  The present invention relates to a method for producing a sucrose carboxylic acid ester. More specifically, the present invention relates to a method for producing a sucrose carboxylic acid ester having a high melting point and excellent handleability.

  Conventionally, sucrose carboxylic acid esters such as sucrose acetate are known to be useful as resin modifiers and the like. Therefore, many methods for producing such sucrose carboxylic acid esters have been proposed.

  Patent Document 1 proposes a method for producing a sucrose carboxylate ester by removing the solvent from the solution containing the sucrose carboxylate ester.

Japanese Patent Laid-Open No. 7-101974

  However, in the method described in Patent Document 1, the melting point of the obtained sucrose carboxylic acid ester is about 45 ° C. and is low. Therefore, the use of such a sucrose carboxylate ester is likely to be limited. It is also known that a sucrose carboxylate having a high melting point can be obtained by precipitating as crystals from a sucrose carboxylate solution. However, the sucrose carboxylic acid ester obtained by removing the solvent from the sucrose carboxylic acid ester solution has a low melting point and poor fluidity, such as a part of the compound melting and blocking during storage. Therefore, such a sucrose carboxylic acid ester has a problem that handling property (workability) is greatly inferior at the time of charging raw materials when used industrially. Moreover, the method of depositing as crystals tends to require a long time for production.

  The present invention has been made in view of such conventional circumstances. A sucrose carboxylic acid ester having a high melting point and excellent workability at the time of use can be obtained by a simple operation within a relatively short time. It aims at providing the manufacturing method of the sucrose carboxylic acid ester for obtaining.

  The method for producing a sucrose carboxylate of the present invention that solves the above problems mainly includes the following constitution.

  (1) A preparation step of preparing a first sucrose carboxylate having a first melting point, and a second sucrose carboxylate having a second melting point higher than the first melting point are separately prepared. A mixing step of mixing the first sucrose carboxylate ester with the second sucrose carboxylate ester at a mixing temperature not lower than the first melting point and lower than the second melting point, and the mixing step. And a holding step of holding the mixture obtained in step 1 at a holding temperature that is equal to or higher than the first melting point and lower than the second melting point for 1 minute or more.

  According to such a configuration, in the method for producing a sucrose carboxylate of the present invention, the second sucrose carboxylate is added to the first sucrose carboxylate and the second sucrose carboxylate is equal to or higher than the first melting point. And a mixing step of mixing at a mixing temperature lower than the melting point. At such a mixing temperature, the first sucrose carboxylate is melted and the second sucrose carboxylate is not melted. Therefore, the second sucrose carboxylic acid ester is appropriately dispersed in the molten first sucrose carboxylic acid ester. Such a mixture is then held for 1 minute or longer at a holding temperature above the first melting point and below the second melting point. Therefore, the first sucrose carboxylic acid ester is likely to be precipitated with the non-molten second sucrose carboxylic acid ester as a nucleus. The melting point of the sucrose carboxylate obtained by precipitation by such a mechanism is from the melting point of the first sucrose carboxylate (first melting point) to the melting point of the second sucrose carboxylate (first melting point). 2 melting point). As a result, the use of the resulting sucrose carboxylic acid ester is difficult to limit because a decrease in fluidity due to blocking or the like is suppressed. Moreover, the obtained sucrose carboxylic acid ester can be obtained as a block-like solid. Such a block-like sucrose carboxylic acid ester has good fluidity and good handleability. Moreover, although a holding process is 1 minute or more, in many cases, time required is shorter than the time required (for example, 24 hours) of the method of depositing sucrose carboxylic acid ester from the conventional solvent. Therefore, according to the method for producing sucrose carboxylic acid, a high melting point sucrose carboxylic acid ester can be obtained by a simple operation (operation of mixing and holding the second sucrose carboxylic acid ester) within a relatively short time. can get.

  (2) In the mixing step, the second sucrose carboxylate has a mass ratio of the first sucrose carboxylate to the second sucrose carboxylate of 50:50 to 99.9. : The method for producing a sucrose carboxylic acid ester according to (1), wherein the mixture is mixed so that the mass ratio is 0.1, preferably the mass ratio is 60:40 to 97: 3.

  According to such a configuration, in the mixing step, the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester are added so that the mass ratio is 50:50 to 99.9: 0.1. Is done. When mixed at such a mass ratio, the resulting sucrose carboxylic acid ester is likely to be raised so that the melting point approaches the second melting point. Moreover, the 2nd sucrose carboxylic acid ester mixed is an appropriate amount, and it is easy to mix with a 1st sucrose carboxylic acid ester uniformly in a mixing process.

  (3) The average degree of esterification of the second sucrose carboxylic acid ester is within a range of ± 3.0 of the average degree of esterification of the first sucrose carboxylic acid ester, and is 8.0 or less. The method for producing a sucrose carboxylic acid ester according to (1) or (2).

  According to such a configuration, the average degree of esterification of the second sucrose carboxylic acid ester is within a range of ± 3.0 of the average degree of esterification of the first sucrose carboxylic acid ester. Thus, when the average degree of esterification of the first sucrose carboxylic acid ester is relatively close to the average degree of esterification of the second sucrose carboxylic acid ester, the resulting sucrose carboxylic acid ester has a second melting point. It is easy to be raised to approach the melting point.

  (4) The method for producing a sucrose carboxylic acid ester according to any one of (1) to (3), wherein the second melting point is 70 to 150 ° C.

  According to such a configuration, the second melting point is 70 to 150 ° C. Therefore, in the mixing step, the mixing temperature that is lower than the second melting point can be set relatively high. As a result, the viscosity of the first sucrose carboxylic acid ester in the molten state can be lowered in the mixing step, and the second sucrose carboxylic acid ester can be easily mixed uniformly.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the sucrose carboxylic acid ester for obtaining sucrose carboxylic acid ester excellent in workability | operativity at the time of use in a comparatively short time by simple operation is provided. be able to.

<Method for producing sucrose carboxylate>
Hereinafter, the manufacturing method of the sucrose carboxylic acid ester of one Embodiment of this invention is demonstrated. The method for producing a sucrose carboxylate comprises a preparation step of preparing a first sucrose carboxylate ester, a mixing step of mixing the first sucrose carboxylate ester and the second sucrose carboxylate ester, Holding step of holding the mixture. That is, in this embodiment, the first sucrose carboxylic acid ester is mixed with the second sucrose carboxylic acid ester and retained, whereby the target sucrose carboxylic acid ester (third sucrose carboxylic acid ester) is retained. ). In this embodiment, in order to distinguish the sucrose carboxylate prepared in the preparation step, the sucrose carboxylate mixed in the mixing step, and the target sucrose carboxylate, The sucrose carboxylic acid ester prepared in the preparation step is called a first sucrose carboxylic acid ester, and the sucrose carboxylic acid ester mixed in the mixing step is called a second sucrose carboxylic acid ester, which is a target product. The sucrose carboxylic acid ester is referred to as a third sucrose carboxylic acid ester. The obtained third sucrose carboxylic acid ester has a high melting point comparable to that of the second sucrose carboxylic acid ester, and has a block shape with excellent handleability. Hereinafter, each process will be described.

<Preparation process>
The preparation step is a step of preparing the first sucrose carboxylic acid ester. The first sucrose carboxylate is a compound obtained by reacting sucrose (sucrose) with an acylating agent, and has a first melting point. Examples of acylating agents include carboxylic acid compounds or reactive derivatives thereof. One or more acylating agents can be used.

  The carboxylic acid compound is a compound having at least one carboxyl group in the molecule, and examples thereof include aromatic carboxylic acids and aliphatic carboxylic acids. Among these, an aliphatic monocarboxylic acid having one carboxyl group is preferable. Examples of such aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid and the like. Among these, C2-C4 aliphatic monocarboxylic acids such as acetic acid, propionic acid, and butyric acid are preferable.

  Examples of the reactive derivative of the carboxylic acid compound include a corresponding acid halide and acid anhydride. Of these, acid anhydrides of aliphatic monocarboxylic acids are preferred. Examples of such acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, and valeric anhydride. Among these, C4-C8 aliphatic monocarboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride are preferable.

  A method for producing the first sucrose carboxylic acid ester from these sucrose and an acylating agent is not particularly limited, and a general-purpose synthesis method is adopted. For example, the first sucrose carboxylate ester is composed of sucrose, the acylating agent described above, and other compounds required for synthesis (for example, basic organic solvents, water-immiscible solvents, various catalysts). , Neutralizing agent, etc.) in the reaction system at a content ratio within a predetermined range, as appropriate, neutralization, distillation under reduced pressure, washing and the like. As a more specific example, the first sucrose carboxylate ester is obtained by reacting sucrose, a basic organic solvent (such as pyridine) and an acylating agent (such as acetic anhydride), and distilling off under reduced pressure. Separate the organic solvent from the acylating agent and, if necessary, reaction by-products. Next, the reaction product is neutralized by mixing a water-immiscible solvent (such as toluene) and a neutralizing agent (such as sodium hydrogen carbonate), and separated to separate the aqueous layer. The remaining organic layer can be prepared by washing as necessary and distilling off under reduced pressure to remove the water-immiscible solvent.

  Examples of the basic organic solvent include morpholine, acetylmorpholine, pyridine, N-methyl-2-pyrrolidone, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2,6-lutidine, piperidine, pyrrolidine, Examples include quinoline and isoquinoline. The basic organic solvent can use 1 type (s) or 2 or more types.

  Examples of water-immiscible solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene, chlorinated aliphatic hydrocarbons such as methylene dichloride, chloroform, carbon tetrachloride, and tetrachloroethylene, diethyl ether, and diisopropyl ether. The lower aliphatic ethers are exemplified. 1 type (s) or 2 or more types can be used for a water-immiscible solvent.

  Examples of the catalyst include a base catalyst and an acid catalyst. Examples of the base catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, trimethylamine, triethylamine and the like. Examples of the acid catalyst include sulfuric acid and hydrogen chloride. The catalyst can use 1 type (s) or 2 or more types. In the present embodiment, when the basic organic solvent described above has a function as a basic catalyst (for example, pyridine), addition of other catalysts may be omitted as appropriate. Moreover, in this embodiment, what has a role as a neutralizer among these catalysts may be used. In this case, for example, even when acetic acid or hydrochloric acid is generated as a reaction by-product, the reaction by-product is neutralized by appropriately reacting with a neutralizing agent dissolved in water added during the liquid separation operation. can do. Examples of such a neutralizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

  The melting point (first melting point) of the obtained first sucrose carboxylate ester is not particularly limited as long as it is lower than the melting point (second melting point) of the second sucrose carboxylate ester described later. As an example, the first melting point is 20 ° C. or higher, preferably 25 ° C. or higher, more preferably 30 ° C. or higher. The first melting point is 60 ° C. or lower, preferably 55 ° C. or lower, more preferably 50 ° C. or lower. When the first melting point is less than 20 ° C., the second melting point tends not to be sufficiently high even when the second sucrose carboxylic acid ester is mixed. On the other hand, when the first melting point exceeds 60 ° C., the first sucrose carboxylic acid ester is not easily melted, and the second sucrose carboxylic acid ester is difficult to mix in the mixing step described later. Tend to get worse.

  The average degree of esterification (first average degree of esterification) of the obtained first sucrose carboxylic acid ester is not particularly limited. When the first average degree of esterification is low, the number of hydroxy groups, which are hydrophilic groups, increases, so that the proportion of sucrose carboxylic acid ester present in the aqueous phase increases during the production process. In this case, it is necessary to recover the sucrose carboxylic acid ester not only from the water-immiscible solvent phase (oil phase) but also from the aqueous phase. Therefore, the first average degree of esterification is preferably not less than a predetermined value, more preferably not less than 4.0, and still more preferably not less than 6.0. The upper limit of the first average degree of esterification is not particularly limited, and may be 8.0 or less, and is preferably 7.9 or less.

  In the present embodiment, the average degree of esterification refers to the average value of the number of esterified alcohols in one molecule of sucrose. The average degree of esterification (Y) can be calculated according to the following formula (I). As described above, in the case of sucrose carboxylate, the upper limit of the average degree of esterification is 8.0. However, when the average degree of esterification is calculated according to the following formula (I), for example, a value calculated by a measurement error or the like may exceed 8.0. In this embodiment, in such a case, the average degree of esterification may be handled as 8.0.

Formula (I): Y = (a × 56110−Ma × X) / [(Mb−Mc) × X + 56110]
(In formula (I), Y is the average degree of esterification, a is the number of hydroxyl groups of sucrose, 8, Ma is the molecular weight of sucrose, 342, X is the average hydroxyl value determined according to JIS K0070, and Mb is (The molecular weight of the carboxylic acid, Mc, represents 18 which is the molecular weight of water.)

  The first sucrose carboxylic acid ester obtained through the preparation step is mixed with the second sucrose carboxylic acid ester separately prepared in the subsequent mixing step.

<Mixing process>
The mixing step is a step of mixing the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester. The second sucrose carboxylic acid ester has a second melting point higher than the first melting point, and is prepared separately from the first sucrose carboxylic acid ester prepared in the preparation step described above. In the mixing step, the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester are mixed at a mixing temperature equal to or higher than the first melting point and lower than the second melting point. Details will be described below.

  The second sucrose carboxylic acid ester is a compound obtained by reacting sucrose (sucrose) with the acylating agent described above.

  The method for producing the second sucrose carboxylic acid ester is not particularly limited, and a general synthesis method is adopted. For example, the content ratio of sucrose, the above-mentioned acylating agent, and other compounds required for synthesis (for example, basic organic solvent, water-miscible solvent, etc.) within a predetermined range in the reaction system. Under reduced pressure, standing or the like. As a specific example, the second sucrose carboxylate ester is obtained by reacting sucrose, a basic organic solvent (such as pyridine) and an acylating agent (such as acetic anhydride), and distilling off under reduced pressure. Separate the solvent and acylating agent. Next, it can be prepared by mixing with a water-miscible solvent (such as methanol) and allowing to stand. According to such a production method, the second sucrose carboxylic acid ester is easily produced in the form of crystals. The crystals of the second sucrose carboxylic acid ester can be mixed as seed crystals in the mixing step. In addition, the 2nd sucrose carboxylate ester should just be a form which is not fuse | melted in a mixing process, and does not need to be a crystal | crystallization. In addition, the second sucrose carboxylic acid ester may be used as it is, a precipitate (third sucrose carboxylic acid ester) obtained through a holding step described later, without depending on the production method. That is, according to the method for producing a sucrose carboxylic acid ester of the present embodiment, the obtained third sucrose carboxylic acid ester has a high melting point similarly to the second sucrose carboxylic acid ester. Therefore, the obtained third sucrose carboxylic acid ester can be used as the second sucrose carboxylic acid ester in a separately performed production process.

  Examples of the water-miscible solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve. One or two or more water-miscible solvents can be used.

  The melting point (second melting point) of the obtained second sucrose carboxylic acid ester is not particularly limited as long as it is higher than the first melting point. For example, the second melting point is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, although it depends on the first melting point. The second melting point is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower, although it depends on the first melting point. When the second melting point is less than 70 ° C., the mixing temperature at the mixing temperature must be set relatively low, and the viscosity of the first sucrose carboxylic acid ester tends to increase. In this case, the first sucrose carboxylic acid ester in the molten state tends to be difficult to uniformly mix with the second sucrose carboxylic acid ester in the non-molten state.

  The average degree of esterification (second average degree of esterification) of the obtained second sucrose carboxylic acid ester is not particularly limited. The second average degree of esterification is preferably not less than a predetermined value, more preferably not less than 4.0, and still more preferably not less than 6.0. The upper limit of the second average degree of esterification is not particularly limited, and may be 8.0 or less, and preferably 7.9 or less.

  The second average degree of esterification is preferably within a range of ± 3.0 of the first average degree of esterification, from the relationship with the first average degree of esterification described above, It is more preferable that it is within the range, and it is even more preferable that it is within the range of ± 0.5. When the second average degree of esterification is within a range of ± 3.0 of the first average degree of esterification, the first average degree of esterification and the second average degree of esterification are relatively close values. Therefore, the melting point of the third sucrose carboxylic acid ester obtained through the holding step described later is easily increased so as to approach the second melting point of the second sucrose carboxylic acid ester.

  The mixing ratio in mixing the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester is not particularly limited. For example, the second sucrose carboxylic acid ester has a mass ratio of the first sucrose carboxylic acid ester to the second sucrose carboxylic acid ester of 50:50 to 99.9: 0.1. It is preferable that they are mixed. In addition, the second sucrose carboxylic acid ester may be mixed so that the mass ratio of the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester is 60:40 to 97: 3. preferable. When the second sucrose carboxylate is mixed so that the mass ratio of the first sucrose carboxylate to the second sucrose carboxylate is 50:50 to 99.9: 0.1 The third sucrose carboxylic acid ester obtained in the holding step, which will be described later, is easily increased so that the melting point (third melting point) approaches the second melting point. Moreover, the 2nd sucrose carboxylic acid ester mixed is an appropriate quantity, and it is easy to mix with a 1st sucrose carboxylic acid ester uniformly in a mixing process. The reason why the second sucrose carboxylate is preferably blended so as to be 50% by mass or less is that the second sucrose carboxylate is in a molten state with respect to the first sucrose carboxylate. From the viewpoint of mixing in a non-molten state, it is difficult to imagine that the blending amount exceeds 50 mass% and is blended as a main component. For these reasons only, the second sucrose carboxylic acid ester may be blended in an amount exceeding 50% by mass.

  The mixing method for mixing the second sucrose carboxylic acid ester with the first sucrose carboxylic acid ester is not particularly limited, and the second sucrose carboxylic acid ester in the molten state is not limited to the second sucrose carboxylic acid ester in the molten state. Any method can be used as long as the sucrose carboxylate can be uniformly mixed. Examples of such a mixing method include a method in which an operator stirs and a method in which a stirrer such as a kneader is used.

  The mixing temperature for mixing the second sucrose carboxylic acid ester with the first sucrose carboxylic acid ester is not particularly limited as long as it is not lower than the first melting point and lower than the second melting point. As an example, the mixing temperature depends on the first melting point and the second melting point described above, but is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. Further, the mixing temperature depends on the first melting point and the second melting point described above, but is preferably 85 ° C. or lower, and more preferably 80 ° C. or lower. When the second sucrose carboxylic acid ester is mixed with the first sucrose carboxylic acid ester at such a mixing temperature, the first sucrose carboxylic acid ester in the molten state maintains the non-molten state. Two sucrose carboxylates can be mixed. In particular, when the mixing temperature is 60 ° C. or higher and 80 ° C. or lower, the second sucrose is prepared by sufficiently melting the first sucrose carboxylic acid ester and appropriately reducing the viscosity of the first sucrose carboxylic acid ester. Since the carboxylic acid ester can be maintained in a non-molten state, the second sucrose carboxylic acid ester is easily mixed uniformly into the first sucrose carboxylic acid ester. In addition, when mixing 2nd sucrose carboxylic acid ester with 1st sucrose carboxylic acid ester, after heating and melting 1st sucrose carboxylic acid ester beforehand, 2nd sucrose carboxylic acid ester The second sucrose carboxylic acid ester may be added to the first sucrose carboxylic acid ester, and then the first sucrose carboxylic acid ester may be heated and melted.

  The mixing time for mixing the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester is not particularly limited, and the second sucrose is contained in the molten first sucrose carboxylic acid ester. What is necessary is just time required in order to mix carboxylic acid ester uniformly to some extent. Such mixing time includes the mixing temperature, the first melting point of the first sucrose carboxylic acid ester, the viscosity of the first sucrose carboxylic acid ester in the molten state, the method of mixing (whether the operator stirs , Whether or not a stirrer such as a kneader is used), etc. Therefore, as an example, the mixing time may be 1 minute or longer, preferably 3 minutes or longer, more preferably 5 minutes or longer. Moreover, as mixing time, 12 hours or less, Preferably it is 5 hours or less, More preferably, 1 hour or less can be mentioned.

  A mixture of the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester obtained through the mixing step (hereinafter simply referred to as a mixture) is held at a predetermined holding temperature in the subsequent holding step.

<Holding process>
The holding step is a step of holding the mixture at a holding temperature that is equal to or higher than the first melting point and lower than the second melting point for one minute or longer. By holding the mixture in the holding step, precipitation of the first sucrose carboxylic acid ester in the mixture is promoted with the second sucrose carboxylic acid ester as a nucleus (the precipitated first sucrose carboxylic acid ester Is referred to as a third sucrose carboxylate ester). At this time, the melting point (first melting point) of the first sucrose carboxylic acid ester is increased and brought close to the melting point (second melting point) of the second sucrose carboxylic acid ester. Details will be described below.

  The holding temperature is not particularly limited as long as it is not lower than the first melting point and lower than the second melting point. For example, the holding temperature depends on the first melting point and the second melting point described above, but is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. Further, the holding temperature depends on the first melting point and the second melting point described above, but is preferably 85 ° C. or lower, and more preferably 80 ° C. or lower. When the mixture is held at such a holding temperature, the first sucrose carboxylic acid ester in the molten state is likely to precipitate using the second sucrose carboxylic acid ester in the non-molten state as a nucleus.

  At this time, the holding temperature may be the same as the mixing temperature or lower than the mixing temperature in comparison with the above-described mixing temperature (that is, the above-described mixing temperature may be higher than the holding temperature). Good). That is, the holding step is a step of holding the mixture at a predetermined holding temperature instead of mixing the mixture. Moreover, the 1st sucrose carboxylic acid ester and the 2nd sucrose carboxylic acid ester are already mixed uniformly by the mixing process. Therefore, in the holding step, the mixture does not need to be stirred for the purpose of stirring uniformly, and may be appropriately stirred for the purpose of, for example, eliminating temperature unevenness in the mixture. As a result, the temperature of the mixture does not necessarily have to be relatively high so as to reduce the viscosity of the mixture in consideration of convenience during mixing. Therefore, it is not necessary to raise the holding temperature as much as the mixing temperature. Thus, since the holding temperature may be a temperature lower than the mixing temperature, temperature management is easy.

  The holding time may be 1 minute or longer, preferably 2 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer. The holding time is preferably 12 hours or shorter, more preferably 10 hours or shorter, and even more preferably 8 hours or shorter. When the holding time is less than 1 minute, the molten first sucrose carboxylic acid ester is not sufficiently precipitated, and the third melting point of the obtained third sucrose carboxylic acid ester is not sufficiently increased. On the other hand, if the holding time exceeds 12 hours, no further increase in the third melting point is expected and production efficiency tends to be difficult to increase.

  In the third sucrose carboxylic acid ester obtained through the above holding step, the third melting point is raised to the same level as the melting point (second melting point) of the second sucrose carboxylic acid ester. Such a high melting point third sucrose carboxylic acid ester suppresses a decrease in fluidity due to blocking or the like. As a result, the use of the third sucrose carboxylic acid ester is unlikely to be limited. The third sucrose carboxylic acid ester can be obtained as a block-like solid. Such a block-like third sucrose carboxylic acid ester has good fluidity and good handleability. Furthermore, although the holding step is 1 minute or more, in many cases, the required time is shorter than the required time (for example, 24 hours) of the conventional method for depositing crystals from a solvent. Therefore, according to the method for producing sucrose carboxylic acid, a high melting point sucrose carboxylic acid ester can be obtained by a simple operation (operation of mixing and holding the second sucrose carboxylic acid ester) within a relatively short time. can get.

<An example of the use of sucrose carboxylate>
According to the method for producing a sucrose carboxylic acid ester of the present embodiment, the obtained third sucrose carboxylic acid ester has a melting point as high as that of a crystal, is in a block shape, has good fluidity and good handling properties. . Therefore, such a 3rd sucrose carboxylic acid ester is utilized for various uses. Hereinafter, an example of an application will be shown.

  The third sucrose carboxylic acid ester is useful as a resin modifier. The sucrose carboxylate ester has an excellent feature that the glossiness of the resin can be improved and the plasticity can be improved. Useful as. Such a resin modifier is used for cosmetics, coloring materials, and the like.

  Examples of the resin containing a sucrose carboxylate as a resin modifier include amorphous resins such as ABS resin, polyvinyl chloride resin, epoxy resin and unsaturated polyester, and crystalline resins such as crystalline polyester resin. Is done. Resin is suitably selected according to a use. The sucrose carboxylic acid ester added to the resin is appropriately selected in accordance with the type and application of the resin and more suitable in terms of the ratio of the low substitution product and the degree of ester substitution.

  The ABS resin is not particularly limited, but polybutadiene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, chlorinated polyethylene, acrylic rubber (methyl acrylate, ethyl acrylate, butyl acrylate, etc.), acrylonitrile, styrene , Obtained by graft polymerization of acrylonitrile, styrene, α-methyl styrene, methyl methacrylate, etc. to a rubbery polymer such as a copolymer with acrylic acid, acrylic acid amide, 2-chloroethyl vinyl ether, etc., acrylonitrile Examples include polybutadiene-styrene graft copolymers. One or more ABS resins can be used.

  The polyvinyl chloride resin is not particularly limited, and is a random copolymer or block copolymer with one or more of vinyl chloride homopolymer resins, chlorinated vinyl chloride resins, and all monomers copolymerizable with vinyl chloride monomers. Vinyl chloride copolymer resins (vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by polymerization, or resins or hydroxyl groups obtained by grafting functional groups such as hydroxyl groups to the above resins Examples are those obtained by reacting a functional group with a reactive compound and graft-bonding them. A polyvinyl chloride resin can use 1 type (s) or 2 or more types.

  The epoxy resin is not particularly limited, and aralkyl type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, phenol biphenyl aralkyl epoxy resin, etc. , Biphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanate Examples thereof include nurate and alicyclic epoxy resin. An epoxy resin can use 1 type (s) or 2 or more types.

  It does not specifically limit as unsaturated polyester resin, What is synthesize | combined by the addition reaction or dehydration condensation reaction of (alpha), (beta) -olefin type unsaturated dicarboxylic acid or its anhydride, and glycol is illustrated. Saturated dicarboxylic acid, aromatic dicarboxylic acid or anhydride thereof, dicyclopentadiene that reacts with carboxylic acid, or the like may be used in combination. Examples of the α, β-olefin unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these dicarboxylic acids. Dicarboxylic acids used in combination with these α, β-olefinic unsaturated dicarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid. An acid etc. are illustrated. Among these, it is preferable to use fumaric acid as the α, β-olefin unsaturated dicarboxylic acid and isophthalic acid as the dicarboxylic acid. One type or two or more types of unsaturated polyester resins can be used.

  The crystalline polyester resin is not particularly limited, but is polyethylene terephthalate, poly-1,4-butylene terephthalate, polyethylene-2,6-naphthalate, polycyclohexanedimethanol terephthalate, poly-1,4-butylene diphenyl-4,4 ′. Examples thereof include crystalline polyesters such as dicarboxylate, polyethyleneoxybenzoate, poly-1,3-propylene terephthalate and poly-1,6-hexylene terephthalate. Among these, polyethylene terephthalate, poly-1,4-butylene terephthalate, and polyethylene-2,6-nanophthalate are preferable. One or more crystalline polyester resins can be used.

  Note that various additives such as impact strength modifiers, stabilizers, lubricants, fillers, pigments, foaming agents, and ultraviolet stabilizers may be added to these resins as necessary.

  As a compounding quantity of 3rd sucrose carboxylic acid ester, it is preferable that it is 1-40 mass% with respect to 100 mass% of resin, and it is more preferable that it is 1-30 mass%. When the amount of the third sucrose carboxylic acid ester is less than 1% by mass, the intended performance tends not to be obtained. On the other hand, when the blending amount of the third sucrose carboxylate exceeds 40% by mass, bleeding out due to long-term storage or the like may occur.

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

<Production Example 1> Production of sucrose acetate crystal 1 A 500 mL separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube was attached to a heating oil bath. Using this separable flask, 50 g (0.15 mol) of sucrose, 570 g (7.2 mol) of pyridine and 120 g (1.18 mol) of acetic anhydride were mixed, and nitrogen gas was bubbled at a flow rate of 10 mL / min. The mixture was reacted at 70 ° C. for 2 hours, and pyridine, unreacted acetic anhydride and by-product acetic acid were distilled off under reduced pressure. To the obtained residue, 220 g of methanol was added and mixed, and the mixture was allowed to stand at −5 ° C. for 18 hours to precipitate crystals. The crystals precipitated by filtering this solution were taken out, washed with 30 g of methanol at -5 ° C., and further dried at 45 ° C. for 8 hours under reduced pressure to give sucrose acetate crystal 1 (second sucrose carboxylic acid An example of an ester, a melting point of 85 ° C. (an example of the second melting point), and an average degree of esterification of 7.9 (an example of the second average degree of esterification)) were obtained.

<Production Example 2> Production of sucrose acetate crystal 2 The same operation as in Production Example 1 was carried out except that the amount of acetic anhydride used was 107 g (1.05 mol). Of sucrose carboxylic acid ester, melting point 85 ° C. (example of second melting point), average degree of esterification 7.0 (example of second average degree of esterification)).

<Production Example 3> Production of sucrose acetate crystal 3 The same operation as in Production Example 1 was carried out except that the amount of acetic anhydride used was 77 g (0.75 mol). Of sucrose carboxylate, melting point 86 ° C. (an example of the second melting point), average degree of esterification 5.0 (an example of the second average degree of esterification)).

<Production Example 4> Production of sucrose propionate crystal 1 The same operation as in Production Example 1 was carried out except that 154 g (1.18 mol) of propionic anhydride was used in place of acetic anhydride to produce sucrose propionate. Crystal 1 (an example of the second sucrose carboxylic acid ester, melting point 88 ° C. (an example of the second melting point), average degree of esterification 7.9 (an example of the second average degree of esterification)) was obtained.

<Manufacture example 5> Manufacture of sucrose butyric acid ester crystal 2 In manufacture example 1, it replaced with acetic anhydride and the same operation was performed except having used 187 g (1.18 mol) of butyric anhydride, and sucrose butyric acid ester crystal 1 ( An example of the second sucrose carboxylic acid ester, melting point 90 ° C. (an example of the second melting point), average degree of esterification 7.9 (an example of the second average degree of esterification)) was obtained.

<Example 1>
A 500 mL separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube was attached to the heating oil bath. Using this separable flask, 50 g (0.15 mol) of sucrose, 570 g (7.2 mol) of pyridine and 120 g (1.18 mol) of acetic anhydride were mixed, and nitrogen gas was bubbled at a flow rate of 10 mL / min. The mixture was reacted at 70 ° C. for 2 hours, and pyridine, unreacted acetic anhydride and by-product acetic acid were distilled off under reduced pressure. Next, 300 g of toluene and 450 g of a 0.5% by mass aqueous sodium hydrogen carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to collect toluene. Subsequently, toluene is distilled off under reduced pressure, and sucrose acetate 1 (an example of a first sucrose carboxylate, melting point 45 ° C. (an example of a first melting point), average esterification degree 7.9 (first An example of an average degree of esterification of 1)) was obtained (preparation step). 90 g of the obtained sucrose acetate 1 was heated to 70 ° C. and melted, 10 g of sucrose acetate crystal 1 was added, and mixed using a stainless steel metal rod for 1 minute (mixing step) ) And a holding temperature of 70 ° C. and a holding time of 5 hours (holding step) to obtain a sucrose acetate ester (an example of a third sucrose carboxylate ester).

<Examples 2-7, Comparative Examples 1-3>
Changed the mixing conditions (mixing ratio and mixing temperature of each component) and holding conditions (holding temperature and holding time) of sucrose acetate 1 and sucrose acetate crystal 1 as shown in Table 1 or Table 2. Except having done, operation similar to Example 1 was performed and the sucrose acetate ester of Examples 2-7 and Comparative Examples 1-3 was obtained.

<Example 8>
In Example 1, the same operation was performed except that the amount of acetic anhydride used was 107 g (1.05 mol), and sucrose acetate ester 2 (an example of the first sucrose carboxylate ester, melting point 45 ° C. (first 1) and an average degree of esterification of 7.0 (an example of the first average degree of esterification)). 90 g of the obtained sucrose acetate ester 2 is heated to 70 ° C. and melted, 10 g of sucrose acetate crystal 2 is added, mixed uniformly, and further maintained at a retention temperature of 70 ° C. and a retention time of 5 hours. And sucrose acetate was obtained.

<Examples 9 to 11 and Comparative Examples 4 to 5>
Changed the mixing conditions (mixing ratio and mixing temperature of each component) and holding conditions (holding temperature and holding time) of sucrose acetate 2 and sucrose acetate crystal 2 as shown in Table 1 or Table 2. Except having carried out, operation similar to Example 8 was performed and the sucrose acetate ester of Examples 9-11 and Comparative Examples 4-5 was obtained.

<Example 12>
In Example 1, 90 g of the obtained sucrose acetate 1 was heated to 70 ° C. and melted, 10 g of sucrose acetate crystal 2 was added, mixed uniformly, and further maintained at a holding temperature of 70 ° C. A sucrose acetate was obtained by performing the same operation except that the retention time was 12 hours.

<Example 13>
In Example 8, 90 g of the obtained sucrose acetate 2 was heated to 70 ° C. and melted, 10 g of sucrose acetate crystal 1 was added, mixed uniformly, and further maintained at a holding temperature of 70 ° C. A sucrose acetate was obtained by performing the same operation except that the retention time was 12 hours.

<Example 14>
In Example 1, the same operation was performed except that the amount of acetic anhydride used was 77 g (0.75 mol), and sucrose acetate 3 (an example of the first sucrose carboxylate ester, melting point 46 ° C. (first 1) and an average degree of esterification of 5.0 (an example of the first average degree of esterification)). 90 g of the obtained sucrose acetate 3 was heated to 70 ° C. and melted, 10 g of sucrose acetate crystal 3 was added, mixed uniformly, and further maintained at a retention temperature of 70 ° C. and a retention time of 3 hours. And sucrose acetate was obtained.

<Example 15>
In Example 1, the same operation was performed except that 154 g (1.18 mol) of propionic anhydride was used instead of acetic anhydride, and sucrose propionate 1 (an example of the first sucrose carboxylate ester, melting point) 48 degreeC (an example of 1st melting | fusing point) and average esterification degree 7.9 (an example of 1st average esterification degree)) were obtained. 90 g of the obtained sucrose propionate 1 was heated to 70 ° C. and melted, 10 g of sucrose propionate crystal 1 was added, mixed uniformly, and further maintained at a retention temperature of 70 ° C. and a retention time of 2 The sucrose propionate was obtained by holding for a while.

<Example 16>
In Example 1, the same operation was performed except that 187 g (1.18 mol) of butyric anhydride was used in place of acetic anhydride, and sucrose butyrate 1 (an example of the first sucrose carboxylate, melting point 50 ° C.) (An example of the first melting point) and an average degree of esterification of 7.9 (an example of the first average degree of esterification)). 90 g of the obtained sucrose butyrate 1 was heated to 70 ° C. and melted, 10 g of sucrose butyrate crystal 1 was added, mixed uniformly, and further maintained at a retention temperature of 70 ° C. and a retention time of 1 hour. The sucrose butyrate ester was obtained.

<Example 17>
Except that the holding conditions (holding temperature and holding time) of sucrose acetate 1 and sucrose acetate crystal 1 were changed as shown in Table 1, the same operation as in Example 1 was carried out. Sucrose acetate was obtained.

<Examples 18 to 19>
Except for changing the holding conditions (holding temperature and holding time) of sucrose acetate ester 2 and sucrose acetate crystal 2 as shown in Table 1, the same operation as in Example 8 was performed, and Examples 18 to 19 sucrose acetates were obtained.

<Example 20>
Except for changing the holding conditions (holding temperature and holding time) of sucrose acetate 1 and sucrose acetate crystal 1 as shown in Table 1, the same operation as in Example 2 was carried out. Sucrose acetate was obtained.

<Examples 21 to 22>
Except having changed the holding conditions (holding temperature and holding time) of the sucrose acetate ester 2 and the sucrose acetate crystal 2 as shown in Table 1, the same operations as in Example 11 were performed, and Examples 21 to 21 were performed. 22 sucrose acetates were obtained.

<Example 23>
In Example 1, 70 g of the obtained sucrose acetate 1 was heated to 70 ° C. and melted, 30 g of sucrose acetate crystal 3 was added, mixed uniformly, and further maintained at a holding temperature of 70 ° C. A sucrose acetate was obtained in the same manner except that the retention time was 8 hours.

<Comparative Example 6>
The sucrose acetate crystal 1 obtained in Production Example 1 was used as the sucrose acetate ester of Comparative Example 6.

<Comparative Example 7>
The sucrose acetate crystal 2 obtained in Production Example 2 was used as the sucrose acetate ester of Comparative Example 7.

  About sucrose carboxylic acid ester obtained in Examples 1-23 and Comparative Examples 1-7, melting | fusing point and fluidity | liquidity were evaluated in accordance with the following evaluation methods. The results are shown in Table 1 or Table 2.

<Evaluation method>
(1) Melting point Measured according to JIS-K0064.
(2) Fluidity 1.0 kg of each of the obtained sucrose carboxylate esters on a stainless steel sieve (aperture 9.5 mm, inner diameter 200 mm × inner height 60 mm, manufactured by AS ONE Co., Ltd.) using a resin hammer Until all the sucrose carboxylate passed through the sieve. The sieved sucrose carboxylate is stored in a 50 ° C. environment for 24 hours, and then placed on a stainless steel sieve (mesh opening 16.0 mm, inner diameter 200 mm × inner height 60 mm, manufactured by AS ONE Co., Ltd.) for 10 seconds. The sample was shaken left and right by hand, and the presence or absence of a residue on the sieve was confirmed.
(Evaluation criteria)
○: No residue.
X: There is a residue.

  As shown in Tables 1 and 2, sucrose acetates 1 to 3, sucrose propionate 1 or sucrose butyrate 1, sucrose acetate crystals 1 to 3, sucrose propionate crystals 1 or According to the production method of Examples 1 to 23, the sucrose butyrate crystal 1 was mixed at a mixing temperature of 45 ° C. or higher and lower than 85 ° C. and held at a holding temperature of 45 ° C. or higher and lower than 85 ° C. for 1 minute or longer. Each of the obtained sucrose carboxylic acid esters had a melting point of 80 ° C. to 90 ° C., and the melting point of each of the mixed sucrose carboxylic acid esters was increased to the same or similar level. Moreover, each obtained sucrose carboxylic acid ester was excellent in fluidity | liquidity. That is, each sucrose carboxylic acid ester obtained by the production method of Examples 1 to 23 passes through a sieve having an aperture of 16.0 mm even after being placed in a 50 ° C. environment in fluidity evaluation. did. That is, these sucrose carboxylate esters do not bind to each other and remain in a block shape even when the working environment becomes hot, such as in summer. Such a block-like sucrose carboxylic acid ester is excellent in fluidity when, for example, a raw material is charged in the production process.

  Among them, in the comparison between Example 1, Example 2 and Example 7 in which only the blending ratio in the mixing step was changed, and in the comparison between Example 10 and Example 11, the blending ratio of sucrose carboxylate crystal was larger. The sucrose carboxylate obtained by the production methods of Example 7 and Example 11 has a melting point higher than that of the sucrose carboxylate obtained by the production methods of Example 1, Example 2, and Example 10. Was expensive. In particular, the melting point of the sucrose carboxylate obtained by the production method of Example 7 was the same as that of the sucrose acetate crystal 1 (85 ° C.).

  Further, in the comparison between Example 3 and Example 7 in which only the holding time in the holding process was changed, and in the comparison between Example 8 and Example 10, the manufacturing method of Example 7 or Example 8 having a long holding time was obtained. The obtained sucrose carboxylate ester had a melting point higher than that of the sucrose carboxylate ester obtained by the production method of Example 3 or Example 10.

  Furthermore, in the comparison between Example 2 and Example 6 and Example 20 in which only the holding temperature in the holding process was changed, and in the comparison between Example 8 and Example 9, Example 6 and Example 9 having a high holding temperature. The sucrose carboxylate obtained by this production method had a higher melting point than the sucrose carboxylate obtained by the production methods of Example 2, Example 20, and Example 8.

  In addition, in the comparison of Examples 1 to 5 in which the blending ratio in the mixing step is changed, the melting point is sufficiently increased even if the holding time is short by increasing the blending ratio of the sucrose carboxylic acid ester crystals to be mixed. I found out that In particular, the sucrose carboxylate obtained by the production method of Example 5 had a retention time of only 1 minute, but the melting point of the obtained sucrose carboxylate was the same as that of sucrose acetate crystal 1. (85 ° C.).

  On the other hand, the melting point of the sucrose acetate obtained by the production methods of Comparative Example 1 and Comparative Example 4 in which the holding time in the holding step was 0.5 minutes was not sufficiently increased. Moreover, the manufacturing method of the comparative example 2, the comparative example 3, and the comparative example 5 which made holding temperature in the holding | maintenance process 40 degrees C or 30 degrees C which is less than melting | fusing point (45 degreeC) of sucrose acetate 1 or sucrose acetate 2 The melting point of the sucrose acetate obtained by 1 was not sufficiently increased. Furthermore, the sucrose acetates obtained by the production methods of Comparative Examples 1 to 5 were bound to each other when stored in a 50 ° C. environment, and the fluidity deteriorated. Moreover, the sucrose acetate obtained in Comparative Examples 6-7 had a fine particle size compared with the sucrose carboxylic acid ester (block shape) obtained by the production method of Examples 1-22. However, although such fine particles have a particle size sufficiently smaller than that of the sieve mesh, the fluidity of the particles themselves is poor. Therefore, clogging occurs on the sieve, resulting in poor fluidity evaluation results.

Claims (5)

The first sucrose carboxylate having a first melting point and the second sucrose carboxylate having a second melting point higher than the first melting point are equal to or higher than the first melting point and the stirring step for stirring at the mixing temperature of less than the second melting point observed including,
The stirring step includes
The first sucrose carboxylate having a first melting point and the second sucrose carboxylate having a second melting point higher than the first melting point are equal to or higher than the first melting point and A mixing step of mixing at a mixing temperature less than the second melting point;
The mixture mixture obtained in step, said first and at least the melting point and the second including a holding step at a holding temperature lower than the melting point is held for more than one minute, the manufacturing method of the sucrose carboxylic acid ester. In the stirring step, the mass ratio of the first sucrose carboxylic acid ester and the second sucrose carboxylic acid ester is 50: 99.9: 0.1, No placement claim 1 Symbol A method for producing a sucrose carboxylate. The average esterification degree of the second sucrose carboxylic acid ester is within a range of ± 3.0 of the average esterification degree of the first sucrose carboxylic acid ester, and is 8.0 or less. A method for producing a sucrose carboxylic acid ester according to claim 1 or 2 . The method for producing a sucrose carboxylic acid ester according to any one of claims 1 to 3 , wherein the second melting point is 70 to 150 ° C. Sucrose carboxylic acid ester obtained by the above stirring process, in separately the stirring step of the manufacturing method of the sucrose carboxylic acid ester to be performed, is used as the second sucrose carboxylic acid ester of claim 1-4 The manufacturing method of the said sucrose carboxylic acid ester of any one.