JP7356142B2 - Method for producing rosin alkoxylate - Google Patents

Description

The present invention relates to a method for producing rosin alkoxylates. More specifically, the present invention relates to a method for producing rosin alkoxylate, which is an AO adduct of rosin, by adding alkylene oxide (hereinafter referred to as "AO") such as ethylene oxide to rosin.

Conventionally, rosin, which is refined from pine resin obtained from the sap of plants in the Pinaceae family, has been refined using alkylene oxides such as ethylene oxide (hereinafter referred to as "EO") and propylene oxide (hereinafter referred to as "PO"). "Rosin alkoxylate", which is an AO adduct of rosin (hereinafter referred to as "AO"), is used in various applications such as emulsifiers, dispersants, and metal oil agents.

Two methods are generally known for producing rosin alkoxylates: one is to add AO to rosin, and the other is to esterify rosin with an AO polymer such as polyethylene glycol or polypropylene glycol. In the former case, the rosin is etherified by adding AO to the rosin as a starting material in the presence of a basic catalyst such as potassium hydroxide (KOH) and reacting it in an autoclave at a heating temperature of 170°C to 180°C. , it is known that AO adducts of rosin are produced (for example, see Patent Document 1 and Patent Document 2).

Rosin is manufactured using pine resin as a raw material. For example, "tall rosin" is produced as a by-product in the process of manufacturing kraft pulp, which is the raw material for paper from pine, and pine resin is treated with steam. Gum rosin, which is obtained by removing the turpentine oil and refining it, and refined wood rosin, which is obtained by finely crushing pine roots, extracting them with a solvent, and removing the turpentine oil from the extract with steam. Mainly known. These are solids that exhibit glassy properties at room temperature, and generally soften at around 75°C to 80°C and become liquid at about 100°C or higher. Further, rosin is generally soluble in solvents such as alcohol, ether, benzene, and chloroform, but is basically insoluble in water.

Japanese Patent Application Publication No. 01-219051 Japanese Patent Application Publication No. 01-219052

As mentioned above, when performing an etherification reaction to synthesize rosin alkoxylate by adding AO to rosin, if the number of moles of AO added to rosin is small, the water solubility of the produced rosin alkoxylate will be low. This is known empirically. Therefore, the produced rosin alkoxylate adheres to the inside of the reaction vessel in which the etherification reaction was carried out, and cleaning after the reaction may not be easy.

On the other hand, the rosin used as the starting material has a relatively low softening point of 80°C, as described above. Therefore, before introducing the rosin into the reaction vessel in which the etherification reaction with AO takes place, the rosin is sometimes introduced into a dissolution vessel in advance, and after being sufficiently dissolved, the rosin is transported to the reaction vessel. During transportation, the temperature in the transportation piping that connects the reaction container and the dissolution container may drop below the softening point, and the rosin may solidify and become clogged inside the transportation piping, or the rosin may become stuck inside the dissolution container. Sometimes it solidified.

As described above, in the method for producing rosin alkoxylates such as rosin ethoxylates, problems with the washability of the produced rosin alkoxylates and problems with solidification of the rosin have sometimes occurred.

Therefore, in view of the above-mentioned circumstances, the present invention improves the washability of the reaction container with water after the reaction when rosin alkoxylate is produced by the etherification reaction of rosin, and also improves the ease of cleaning the reaction vessel with water when transporting the dissolved rosin. An object of the present invention is to provide a method for producing rosin alkoxylate that can prevent rosin from solidifying in transportation piping or the like.

The inventors of the present application have conducted intensive research to solve the above problems, and have found that in the production of rosin alkoxylate by etherification reaction, by mixing a compound that can be etherified with rosin, it has good washability with water. In addition, we have discovered a method for producing rosin alkoxylates that can prevent rosin from solidifying during transportation.

That is, the method for producing rosin alkoxylate of the present invention includes a mixture (A) composed of rosin, a compound that can be etherified with the rosin, has active hydrogen in the molecule, and is liquid at 40°C. A step of introducing the compound (B), which exhibits the properties of A dissolution condition adjustment step of adjusting the dissolution conditions to specified temperature and pressure, and dissolving the mixture (A) and the compound (B) in the dissolution container adjusted to the dissolution conditions to produce a dissolved mixture. a compound introduction step of introducing the generated dissolved mixture into a reaction container; a reaction initial condition adjustment step of adjusting the inside of the reaction container to predetermined reaction initial conditions of temperature and pressure; Using the reaction vessel adjusted to the initial reaction conditions, the compound (C) composed of alkylene oxide is added to the dissolved mixture , and the etherification reaction is carried out under the etherification reaction conditions of the specified temperature and pressure to form the rosin alkoxylate. and an etherification reaction step.

Here, the rosin used as the mixture (A) is not particularly limited, but includes, for example, natural rosin produced from pines, isomerized rosin, dimerized rosin, polymerized rosin, disproportionated rosin, Rosins containing abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, lepopimaric acid, etc. as main components, such as rosin, can be used. As mentioned above, among natural rosins, "tall rosin", "gum rosin", "wood rosin", etc. are known, but in the method for producing rosin alkoxylate of the present invention, especially "gum rosin" is used. Preferred for use.

On the other hand, compound (B) is capable of undergoing an etherification reaction with the rosin, has active hydrogen in the compound, and exhibits liquid properties at 40°C. For example, linear alcohols with 1 to 14 carbon atoms such as methanol, ethanol, propanol, butanol, hexanol, alcohols with branched structures of 3 to 22 carbon atoms, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polypropylene glycol, etc. glycols, polyhydric alcohols such as glycerin, diglycerin, and polyglycerin, phenol, alkylphenol having an alkyl group having 1 to 24 carbon atoms, phenols such as (mono-, di-, and tri-)styrenated phenol, monoethanolamine , diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoalkylamine and dialkylamine having an alkyl group having 1 to 22 carbon atoms, and AO adducts of these compounds. Can be mentioned.

On the other hand, compound (C) is an alkylene oxide, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, tetrahydrofuran, and 1,2-epoxycyclohexane. Among them, ethylene oxide and propylene oxide are preferred.

These mixture (A) and compound (B) are each introduced into a reaction vessel at a predetermined mixing ratio (compound introduction step), and the initial reaction conditions of the predefined temperature and pressure in the reaction vessel are met. In this state, compound (C) is added, and the etherification reaction is carried out under the etherification reaction conditions of specified temperature and pressure (etherification reaction step). Since compound (C) generates a large amount of heat when it reacts, compound (C) is added to the system mixed with mixture (A) and compound (B) in the etherification reaction process under the etherification reaction conditions. It is preferable to add it gradually while maintaining the Note that a catalyst may be mixed in the etherification reaction step.

A rosin alkoxylate , which is an AO adduct of rosin, is produced by adding a compound (C) consisting of an alkylene oxide to rosin, which is the mixture (A). Furthermore, an etherified product of compound (B) (hereinafter simply referred to as "etherified product"), in which compound (B) is etherified, is produced together with the rosin alkoxylate.

As shown above, the etherified product is produced by introducing the compound (B) together with the rosin into the reaction vessel. As a result, the rosin alkoxylate is prevented from adhering to the interior of the reaction vessel, etc., and its water solubility is increased, making it possible to wash with water or the like. Thereby, operations such as cleaning the reaction container can be simplified, and production efficiency can be improved and working time can be shortened.

Furthermore, in the method for producing rosin alkoxylate of the present invention, compound (B) is constituted by a compound shown in Chemical Formula 1 below.

Here, in the above chemical formula 1, R ¹ is a hydroxyl group, a residue obtained by removing active hydrogen from an alkyl alcohol having 1 to 30 carbon atoms, a residue obtained by removing active hydrogen from an alkenyl alcohol having 2 to 30 carbon atoms, or a residue obtained by removing active hydrogen from an alkenyl alcohol having 2 to 30 carbon atoms, and 6 carbon atoms. Residues obtained by removing active hydrogen from ~30 phenols, residues obtained by removing active hydrogen from polyhydric alcohols having 3 to 30 carbon atoms, active hydrogen from amines having nitrogen atoms, and alkyl groups having 1 to 22 carbon atoms. AO is an oxyalkylene group having 2 to 18 carbon atoms, indicating that 50 mol% or more of the total is ethylene oxide, and m is an integer of 0 to 20. , n represents an integer of 1 to 6, m×n represents 0 to 20, and R ¹ is a residue obtained by removing active hydrogen from an amine having a nitrogen atom or an alkyl group having 1 to 22 carbon atoms. In the case of , m is 0 and m×n is exclusive of 0 .

Here, in the above formula 1, R ¹ is preferably a residue obtained by removing active hydrogen from an alkyl alcohol having 6 to 20 carbon atoms, a residue obtained by removing active hydrogen from an alkenyl alcohol having 6 to 20 carbon atoms, or a residue obtained by removing active hydrogen from an alkenyl alcohol having 6 to 20 carbon atoms. It further shows either a residue obtained by removing active hydrogen from a phenol having 6 to 30 carbon atoms, or a residue obtained by removing active hydrogen from an alkylamine having 6 to 20 carbon atoms.

In the above chemical formula 1, AO is further preferably composed of only ethylene oxide and propylene oxide, and it is more preferable that ethylene oxide is 90 mol % or more.

Furthermore, in the method for producing rosin alkoxylate of the present invention, the conditions adjusted in the reaction initial condition adjustment step are not limited to temperature, and can be performed under arbitrary pressure conditions. Among these, in order to react the rosin in a fluid state, the temperature is preferably 80 to 200°C and the pressure is preferably 0.0 to 10 MPa in gauge pressure. Outside this range, the reaction rate may be insufficient or the reaction may run out of control. The temperature is preferably 100-180°C. The pressure is preferably 0.0 to 1.0 MPa, more preferably 0.1 to 0.9 MPa in gauge pressure.

Furthermore, in the method for producing rosin alkoxylate of the present invention, the etherification reaction conditions adjusted in the etherification reaction step are not limited to temperature, and can be carried out under arbitrary pressure conditions. The conditions may be the same as those in the reaction initial condition adjustment step, or different conditions may be used. Among these, in order to react the rosin in a fluid state, the temperature is preferably 80 to 200°C and the pressure is preferably 0.0 to 10 MPa in gauge pressure. Outside this range, the reaction rate may be insufficient or the reaction may run out of control. The temperature is preferably 100-180°C. The pressure is preferably 0.0 to 1.0 MPa, more preferably 0.1 to 0.9 MPa in gauge pressure. Since the etherification reaction is an exothermic reaction, the temperature and pressure under the etherification reaction conditions are preferably the same or higher than the temperature and pressure under the initial reaction conditions.

Furthermore, in the method for producing rosin alkoxylate of the present invention, there is a step of introducing the mixture (A) and the compound (B) into the dissolution container, and the inside of the dissolution container is heated to a predetermined temperature. Further comprising a dissolution condition adjustment step of adjusting the dissolution conditions of pressure, and a dissolution step of dissolving the mixture (A) and the compound (B) in a dissolution container adjusted to the dissolution conditions to produce a dissolved mixture. In the compound introduction step, the generated dissolved mixture is introduced into the reaction vessel as a mixture of mixture (A) and compound (B) . Note that the catalyst may be mixed in any one of the dissolution container introduction step, the dissolution step, and the compound introduction step.

Furthermore, in the method for producing rosin alkoxylate of the present invention, the melting conditions adjusted in the melting condition adjustment step include a melting temperature of 80 to 200°C and a melting pressure of -0.01 to 1.0 MPa in gauge pressure. There may be. A negative gauge pressure means that the test is performed under reduced pressure. It is more preferable to reduce the pressure using a vacuum pump or the like and perform a dehydration operation in the dissolution condition adjustment step.

Furthermore, in the rosin alkoxylate manufacturing method of the present invention, a catalyst may be added to the reaction vessel in the etherification reaction step, and etherification may be performed in the presence of the catalyst. As the catalyst, known catalysts such as acid catalysts, base catalysts (alkali catalysts), and coordination metal catalysts can be used. Examples of the acid catalyst include Brønsted acids such as sulfuric acid and phosphoric acid, as well as Lewis acids such as boron trifluoride, aluminum chloride, and organic aluminum. Base catalysts include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal hydrides such as sodium hydride, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, and alkali metals such as sodium metal. etc. Examples of coordination metal catalysts include multimetal cyanide complexes (DMC) and the like. Preferably, it is an alkali catalyst, and more preferably one or more selected from sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium tert-butoxide.

Furthermore, in the method for producing rosin alkoxylate of the present invention, the above-mentioned etherification catalyst may be added to a dissolution vessel and transported to a reaction vessel together with the dissolution mixture. That is, the etherification catalyst such as potassium hydroxide may be introduced into a dissolution container in advance and transported into the reaction container together with the dissolved mixture of mixture (A) and compound (B). It is preferable to use a catalyst also because the reaction rate becomes faster when a catalyst is used.

According to the method for producing rosin alkoxylate of the present invention, when producing rosin alkoxylate such as rosin ethoxylate by etherification of rosin, rosin alkoxylate is placed inside the reaction vessel or piping after the etherification reaction. can be easily cleaned with water.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram showing the flow of a method for producing rosin alkoxylate of the present invention and a schematic configuration of a production apparatus. It is an explanatory view showing the flow of another example of composition of the manufacturing method of rosin alkoxylate of the present invention, and the schematic composition of a manufacturing device.

Hereinafter, in order to make the configuration and effects of the present invention more specific, the following embodiments and examples will be shown, but the present invention is not limited to these embodiments and examples. In the following embodiments, examples, and comparative examples, unless otherwise specified, "part" means "part by mass" and "%" means mass %.

1. Method for producing rosin alkoxylates Method 1 for producing rosin alkoxylates (hereinafter simply referred to as "Production method 1") according to an embodiment of the present invention, as shown in FIG. (B) is used as the starting material 2, and a compound introduction step S1 in which the starting material 2 is introduced from the compound introduction port 4 of the reaction container 3 based on a predefined blending ratio, and a container of the reaction container 3. Reaction initial condition adjustment step S2 of adjusting the interior to reaction initial conditions RSC of specified temperature and pressure, and adding compound (C) under the adjusted reaction initial conditions RSC, and mixing mixture (A) and compound (B). The process mainly includes an etherification reaction step S3 in which etherification is performed under etherification reaction conditions ERC.

Here, FIG. 1 is an explanatory diagram showing the flow of manufacturing method 1 of the present embodiment and the schematic configuration of manufacturing apparatus PD1 used in manufacturing method 1 to manufacture rosin alkoxylate RA.

In the production method 1 of the present embodiment, in the compound introduction step S1, the starting material 2 such as the mixture (A) is introduced and a catalyst 5 such as potassium hydroxide (corresponding to the etherification catalyst in the present invention) is reacted. It is added to container 3. This promotes the etherification reaction of mixture (A) and the like.

Further, as the reaction initial conditions RSC adjusted in the reaction initial condition adjustment step S2, the temperature can be set to 120° C. and the gauge pressure can be set to 0.01 MPa, for example. In addition to the reaction initial conditions RSC, the interior of the reaction vessel 3 is replaced with nitrogen gas and adjusted so that the reaction is performed under a nitrogen gas (N ₂ ) atmosphere. These reaction initial conditions RSC are merely examples, and the reaction initial conditions RSC in the production method 1 of the present invention are not limited thereto.

After the initial reaction conditions are RSC, compound (C) is introduced and the etherification reaction step S3 is carried out under the etherification reaction conditions ERC. The etherification reaction conditions ERC can be set, for example, at a temperature of 155±10° C. and a gauge pressure of 0.4 MPa. These etherification reaction conditions ERC are merely examples, and the etherification reaction conditions ERC in production method 1 of the present invention are not limited thereto.

Here, the heating device, heating method, pressure adjustment mechanism and pressure adjustment method for heating the inside of the reaction container 3 and adjusting the pressure, as well as the replacement mechanism for substituting nitrogen gas atmosphere, etc. are conventional. It is possible to use well-known techniques and devices, etc., and detailed explanations will be omitted here.

In the production method 1 of the present embodiment, after carrying out the etherification reaction step S3 under the etherification reaction conditions ERC, an aging step etc. is performed as appropriate, the temperature of the reaction vessel 3 is cooled to 90°C, and the reaction product produced is The reaction system further includes a cooling and taking-out step S4 in which the products (rosin alkoxylate RA and etherified compound (B) SB) are taken out of the reaction vessel 3. Here, the cooling extraction step S4 is performed via the extraction pipe 6 communicating with the lower part of the reaction vessel 3. That is, the rosin alkoxylate RA and the like are taken out from inside the reaction vessel 3 through the takeout piping 6.

Furthermore, in the manufacturing method 1 of the present embodiment, after the rosin alkoxylate RA and the like are taken out from the reaction container 3 as described above, rosin alkoxylates attached or remaining inside the reaction container 3 and inside the extraction piping 6 are removed. A water washing step S5 may be included in which the rate RA and the ether compound SB are removed and washed with water.

In addition, in order to evaluate the cleaning performance of rosin alkoxylate RA by the water washing step S5, as shown in FIG. An evaluation position P3 and an evaluation position P4 are set, respectively, in order to visually check the presence or absence and state of adhesion of rosin alkoxylate RA after cleaning. Details of the occlusion evaluation and the cleansing evaluation will be described later.

As explained above, according to the manufacturing method 1 of the present embodiment, the etheratizable compound (B) is introduced into the reaction vessel 3 together with the mixture (A) (rosin), and a compound such as AO is further introduced into the reaction vessel 3. Rosin alkoxylate RA can be produced by adding (C) and a catalyst 5 such as potassium hydroxide, adjusting to predetermined initial reaction conditions RSC, and carrying out an etherification reaction under etherification reaction conditions ERC. can. At this time, by adding the compound (B) together with the rosin, it is possible to suppress the decrease in water solubility that occurs when the number of moles of AO added to the rosin is small, as in the conventional case. Thereby, the inside of the reaction vessel 3 after the etherification reaction can be easily washed with water or the like.

2. Method for producing a rosin alkoxylate having a different structure On the other hand, a method for producing a rosin alkoxylate having a different structure according to the present invention 1a (hereinafter simply referred to as "manufacturing method 1a") involves mixing as shown in FIG. The first starting material 2a for compound (A) and compound (B) is introduced from the dissolution inlet 8 of the dissolution container 7 based on a predefined blending ratio. A dissolution container introduction step T1 in which the dissolution container is introduced, a dissolution condition adjustment step T2 in which the inside of the dissolution container 7 is adjusted to a dissolution condition SC that applies to a prescribed dissolution temperature and dissolution pressure, and a mixture ( The method further includes a dissolution step T3 of dissolving A) and compound (B) to produce a dissolution mixture 9.

Here, FIG. 2 is an explanatory diagram showing the flow of a manufacturing method 1a having a different configuration of the present invention, and also showing a schematic configuration of a manufacturing apparatus PD2 for manufacturing rosin alkoxylate RA, which is used in the manufacturing method 1a. be. Note that components having the same configuration as those in manufacturing method 1 described above are given the same reference numerals, and detailed description thereof will be omitted.

Then, a dissolved mixture 9 produced by dissolving and mixing the dissolved substance (A) and the dissolved substance (B) is introduced into the reaction vessel 3 in the compound introduction step S1 in the production method 1 described above. Note that the steps after the compound introduction step S1 are substantially the same as the manufacturing method 1a and manufacturing apparatus PD1 that have already been described. Detailed explanation of the following will be omitted.

Further, as the melting conditions adjusted in the melting condition adjustment step T2, for example, the melting temperature can be set to 80 to 200° C., and the melting pressure can be set to -0.01 to 1.0 MPa in gauge pressure. In addition to the dissolution conditions SC for dissolving the first starting material 2a and the like, the interior of the dissolution container 7 is adjusted so that the dissolution is carried out under an atmospheric atmosphere, and the dissolution time is set to one hour. The present invention is not limited to these dissolution conditions SC, and the dissolution conditions SC in the production method 1a of the present invention are not limited to these. In addition, conventionally well-known techniques and devices can be used for the heating device, heating method, pressure adjustment mechanism, pressure adjustment method, etc. for heating the inside of the melting container 7 and adjusting the melting pressure. It is.

In order to transport the generated dissolved mixture 9 from the dissolution container 7 to the reaction container 3, a transport pipe 10 that communicates between the dissolution container 7 and the reaction container 3 is provided in the manufacturing apparatus PD2. Furthermore, according to the manufacturing method 1a having a different configuration, the water washing step S5, which is performed after the rosin alkoxylate RA etc. are finally taken out from the reaction container 3 via the extraction pipe 6, is carried out in the water washing step S5. In addition to the inside of the container and the inside of the extraction pipe 6, the inside of the dissolution container 7 and the inside of the transport pipe 10 are cleaned with water.

Furthermore, as shown in FIG. 2, in order to evaluate the cleanability of rosin alkoxylate RA, after cleaning, a specific point inside the dissolution container 7 and a specific point inside the transport piping 10 are placed. An evaluation position P1 and an evaluation position P2 are respectively set in order to visually check the presence or absence of adhesion of rosin alkoxylate RA and the adhesion state. Details of the occlusion evaluation and the cleansing evaluation will be described later.

In addition, in the production method 1a, a catalyst 5 such as potassium hydroxide added to promote the etherification reaction is added to the dissolution container 7 together with the first starting material 2a, and is transported to the reaction container 3 together with the dissolved mixture 9. Alternatively, it may be added directly to the reaction vessel 3 together with the second starting material (compound (C)).

1. Regarding the mixture (A), compound (B), compound (C), and catalyst As shown in Table 1 below, the mixture (A), compound (B), and compound (C) used as starting materials were Rosin alkoxylates were produced (synthesized) for each of the combinations, Examples 1 to 5, Reference Examples 1 to 6 , and Comparative Examples 1 and 2. Here, in Examples 1 to 5, Reference Examples 1 to 2, 4 to 6 , and Comparative Examples 1 and 2, "Gum Rosin Reference Example 3 uses "abietic acid" as the rosin. As described above, rosin such as Gum Rosin

On the other hand, as for compound (B), as shown in Table 1, the compound specified in the method for producing rosin alkoxylate of the present invention is used in Examples 1 to 5 and Reference Examples 1 to 6 , and Comparative Example 1, Sample No. 2 does not use a compound corresponding to compound (B). Note that the compounds (B) used in Example 1 and the like all have a melting point of 40° C. or lower and exhibit liquid properties at room temperature. Furthermore, as shown in Table 1, the mass ratio of the mixture (A) and the compound (B) varies between mixture (A)/compound (B) = 80/20 and 96/4. I'm letting you do that.

Further, as a catalyst used to promote the etherification reaction, potassium hydroxide (KOH) was used in Examples 1 to 4, Reference Examples 1 to 3 , and Comparative Examples 1 and 2, and in Example 5, Reference example 5 uses sodium hydroxide (NaOH), reference example 4 uses sodium methoxide (CH ₃ ONa), and reference example 6 uses potassium tert-butoxide (tBuOK). The amount of the mixture (A), compound (B), compound (C), and catalyst was adjusted so that the total amount was 1000 kg.

2. Regarding production equipment and production method Rosin alkoxylates were produced using two production equipment in Examples 1 to 5, Reference Examples 1 to 6 , and Comparative Examples 1 and 2 (see FIGS. 1 and 2). That is, there is a manufacturing device PD2 (see FIG. 2) that includes a dissolution container and a reaction container and connects the dissolution container and the reaction container with a transfer pipe, and a manufacturing device PD1 that uses only the reaction container (see FIG. 1). ) was used. In Table 1 above, PD1 and PD2 in the manufacturing equipment section indicate that the manufacturing equipment shown in FIGS. 1 and 2 above was used, respectively.

2.1 Method for producing rosin alkoxylate using production apparatus PD2 In Examples 1 to 5 and Comparative Example 1, rosin alkoxylate was produced using production apparatus PD2 equipped with a dissolution container and a reaction vessel. In such a case, the mixture (A), the compound (B) and a 48% potassium hydroxide aqueous solution are introduced into a dissolution container so as to account for 1% of the total mass of the mixture (A) and the compound (B), Dissolution and dehydration were carried out for 1 hour under dissolution conditions in which the dissolution temperature was set to 120° C. and the dissolution pressure was set to gauge pressure -0.05 MPa. As a result, the mixture (A) heated above the softening point (=gum rosin As a result, a molten mixture is produced.

Next, the generated dissolved mixture is transported to a reaction vessel (stainless steel pressure vessel with a nominal volume of 1000 L) via a transport pipe (stainless steel pipe with an outer diameter of 1.5 inches, length 3 m). After replacing the inside of the reaction vessel with nitrogen, the initial reaction conditions were set to a temperature of 120°C and a gauge pressure of 0.01 MPa, and compound (C) was gradually added to the ether at a temperature of 155±10°C and a gauge pressure of 0.4 MPa. The reaction conditions were maintained under pressure. After the injection is completed, aging is carried out for 1 hour at the same temperature and pressure. After the etherification reaction was completed, the temperature of the reaction vessel was cooled to 90° C. or lower, and then the produced rosin alkoxylate and the like were taken out from the reaction vessel.

2.2 Method for producing rosin alkoxylate using production apparatus PD1
In Reference Examples 1 to 5 and Comparative Example 2, rosin alkoxylates were produced using a production apparatus PD1 consisting only of a reaction vessel (a stainless steel pressure vessel with a nominal volume of 1000 L). In such a case, the mixture (A), the compound (B), and the catalyst were introduced into a reaction vessel, and a dehydration reaction was carried out at 120° C. and a gauge pressure of −0.05 MPa for 1 hour. After purging the inside of the reaction vessel with nitrogen, the initial reaction conditions were a temperature of 120°C and a gauge pressure of 0.01 MPa, and compound (C) was gradually added to the etherification reaction conditions of a temperature of 155 ± 10°C and a gauge pressure of 0.4 MPa. It was press-fitted while maintaining the After the injection was completed, aging was carried out for 1 hour at the same temperature and pressure, and after the reaction was completed, the temperature of the reaction vessel was cooled to 90° C. or less, and the produced rosin alkoxylate etc. were taken out from the reaction vessel.

3. Regarding evaluation of occlusiveness and evaluation of cleanability For Examples 1 to 5, Reference Examples 1 to 6 , and Comparative Examples 1 and 2, after producing rosin alkoxylate by the above production method, the production apparatus PD1 after the reaction was completed. , blockage (P2, P4 only) and cleanability of each evaluation position P1, P2, P3, P4 (see Fig. 1 and Fig. 2) in the dissolution container, transport piping, reaction container, and extraction piping of PD2. (P1, P2, P3, P4) were evaluated.

Here, the evaluation criteria for evaluating obstructiveness are:
A: Can be transported without special operations B: Can be transported by heating the piping with low-pressure steam C: Cannot be transported even by heating the piping with low-pressure steam and applying vibration.

On the other hand, the evaluation criteria for cleaning performance evaluation are:
A: It is possible to clean the deposits with water only. B: It is possible to clean the deposits with a 1% aqueous solution of potassium. C: It is possible to clean the deposits with methanol.

Table 1 above shows the results of the occlusion evaluation and the cleanability evaluation of Examples 1 to 5, Reference Examples 1 to 6 , and Comparative Examples 1 and 2. When rosin alkoxylates were produced using the production apparatus PD2 (Examples 1 to 5), the occlusion evaluation was "A" in all cases, and the detergency evaluation was "A" in Examples 1 to 4. , Example 5 was "B". That is, it was confirmed that all of them exhibited occlusive properties and cleansing properties to a level that caused no practical problems.

In the case of Example 5, methyl diglycol was used as the compound (B), and since the methyl group has weak hydrophobicity, it was not possible to clean the deposits with water alone at any of the evaluation positions P1, P2, P3, and P4. First, since it is necessary to use a 1% caustic potassium aqueous solution, the evaluation standard is "B". In addition, in the case of Comparative Example 1 in which rosin alkoxylate was similarly produced using the production apparatus PD2, the occlusiveness evaluation was "C" at the evaluation positions P1 and P2 because the compound (B) was not used. In this case, even if the piping was heated with low-pressure steam or vibrations such as tapping were applied to the deposits, the deposits could not be transferred from the melting container 7 to the reaction container 3. Therefore, the cleaning performance evaluation at the evaluation positions P3 and P4 is indicated by "-" as being impossible to evaluate.

On the other hand, when rosin alkoxylates were produced using production apparatus PD1 ( Reference Examples 1 to 5 ), the detergency evaluation was "A" for Reference Examples 1 to 3 , and on the other hand, for Reference Examples 4 to 6 . The detergency evaluation was "B". That is, it was confirmed that all of them exhibited a level of cleansing performance that caused no practical problems. In addition, as shown in Reference Example 3 , it was shown that abietic acid can be used as the mixture (A), and furthermore, as the compound (B), methyl diglycol, N-methyl The possibility of using diethanolamine and tetraethylene glycol was confirmed. In addition, in the case of Comparative Example 2 in which rosin alkoxylate was similarly produced using production apparatus PD2, the detergency evaluation was "C" at evaluation positions P3 and P4 because compound (B) was not used.

1, 1a: Manufacturing method of rosin alkoxylate (manufacturing method), 2: Starting material, 2a: First starting material, 2b: Second starting material, 3: Reaction vessel, 4: Compound inlet, 5: Catalyst (ether catalyst), 6: extraction piping, 7: dissolution container, 8: dissolution inlet, 9: dissolved mixture, 10: conveyance piping, ERC: etherification reaction conditions, P1, P2, P3, P4: evaluation Position, PD1, PD2: Production equipment, RA: Rosin alkoxylate, RSC: Initial reaction conditions, S1: Compound introduction step, S2: Initial reaction condition adjustment step, S3: Etherification reaction step, S4: Cooling removal step, S5: Water washing step, SB: etherified product, SC: dissolution conditions, T1: dissolution container introduction step, T2: dissolution condition adjustment step, T3: dissolution step.

Claims (7)

A mixture (A) composed of rosin, which is a compound that can be etherified together with the rosin, has active hydrogen in the molecule, exhibits liquid properties at 40°C, and is represented by the following chemical formula 1. a dissolution container introduction step of introducing the compound (B) composed of the compounds into the dissolution container at a predetermined blending ratio;
a melting condition adjustment step of adjusting the inside of the melting container to predefined melting conditions of temperature and pressure;
a dissolving step of dissolving the mixture (A) and the compound (B) in the dissolution container adjusted to the dissolution conditions to produce a dissolved mixture;
a compound introduction step of introducing the generated dissolved mixture into a reaction container;
a reaction initial condition adjustment step of adjusting the inside of the reaction container to predetermined reaction initial conditions of temperature and pressure;
Using the reaction vessel adjusted to the initial reaction conditions, the compound (C) composed of alkylene oxide is added to the dissolved mixture , and the etherification reaction is carried out under the etherification reaction conditions of the specified temperature and pressure to form a rosin alkoxylate. and an etherification reaction step for producing rosin alkoxylate.

(R ¹ is a hydroxyl group, a residue obtained by removing active hydrogen from an alkyl alcohol having 1 to 30 carbon atoms, a residue obtained by removing active hydrogen from an alkenyl alcohol having 2 to 30 carbon atoms, or a phenol having 6 to 30 carbon atoms. Residues from which active hydrogen has been removed, residues from which active hydrogen has been removed from polyhydric alcohols having 3 to 30 carbon atoms, and residues from which active hydrogen has been removed from amines having nitrogen atoms and alkyl groups having from 1 to 22 carbon atoms. AO is an oxyalkylene group having 2 to 18 carbon atoms, indicating that 50 mol% or more of the total is ethylene oxide, m is an integer of 0 to 20, and n is 1 represents an integer of ~6, m x n represents 0 ~ 20, and R ¹ is a residue obtained by removing active hydrogen from an amine having a nitrogen atom or an alkyl group having 1 to 22 carbon atoms, m is 0, (m×n excludes 0.) In the above chemical formula 1, R ¹ is a residue obtained by removing active hydrogen from an alkyl alcohol having 6 to 20 carbon atoms, a residue obtained by removing active hydrogen from an alkenyl alcohol having 6 to 20 carbon atoms, or a phenol having 6 to 30 carbon atoms. The rosin alkoxylate according to claim 1, wherein the rosin alkoxylate according to claim 1 is one or more of the following: a residue obtained by removing active hydrogen from amine having an alkyl group having 6 to 20 carbon atoms; Manufacturing method . The method for producing rosin alkoxylate according to claim 1 or 2 , wherein the etherification reaction step is performed in the presence of an etherification catalyst . The method for producing rosin alkoxylate according to claim 3 , wherein the etherification catalyst is an alkali catalyst . The method for producing a rosin alkoxylate according to any one of claims 1 to 4 , wherein in the chemical formula 1, the AO is composed only of ethylene oxide and propylene oxide, and the ethylene oxide is 90 mol% or more . The rosin alkoxylate according to any one of claims 3 to 5 , wherein the etherification catalyst is one or more selected from sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium tert-butoxide. Production method. The rosin used as the mixture (A) is
The method for producing a rosin alkoxylate according to any one of claims 1 to 6, wherein the rosin alkoxylate is gum rosin .

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