JPH05271621A - Production of colorless rosin - Google Patents

Abstract

PURPOSE:To improve color tone, odor, and stability by subjecting a purified rosin to disproportionation and dehydrogenation in the presence of a catalyst and adding an organophosphorus compound to the resulting reaction system. CONSTITUTION:A crude rosin is dissolved in a good solvent and the solution is distilled at 1-10mmHg and 200-300 deg.C to obtain a purified rosin (a). The rosin (a) is disproportionated and dehydrogenated in the presence of a catalyst in an amount of 0.01-5wt.% based on the rosin (a) at an initial hydrogen pressure of 10kg/cm<2> or lower at 100-300 deg.C to obtain a rosin-derived resin acid composition comprising 15-35wt.% dihydroabietic acid and 85-65wt.% dehydroabietic acid. To this reactional system is added an organophosphorus compound represented by the formula (R-O-)3-P (wherein R is a 1-12C alkyl, phenyl, or a dialkylphenyl having a 1-12C alkyl) in an amount of 0.01-1.0wt.% based on the rosin (a).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing rosin which is colorless, odorless and excellent in heat stability.

[0002]

BACKGROUND OF THE INVENTION Rosin and its derivatives, rosin esters, have been used for tackifiers for adhesives, modifiers of rubbers and various plastics, resins for traffic paints, sizing agents for papermaking, and synthetic rubbers. It is used in various applications as a raw material for emulsifiers, ink resins, paint resins, etc. However, the rosin compound is colored yellow to yellowish brown in appearance, and is not satisfactory in terms of odor, heat stability, weather resistance (hereinafter referred to as stability) and the like.

Therefore, in order to solve the above-mentioned drawbacks of the rosin-based compound, disproportionated rosin is disproportionated to improve the thermal stability. Hydrogenated rosins having improved properties, or esterified products using the disproportionated rosins or hydrogenated rosins are commercially available, but all of them are insufficient in terms of color tone and stability.

Further, JP-B-45-33771 and JP-B-49-20599 describe a method of disproportionating a rosin or a rosin compound with a specific organic sulfur compound. The disproportionated rosin obtained is also insufficient in terms of color tone, odor and stability.

As described above, none of the conventional rosins, disproportionated rosins, and hydrogenated rosins can simultaneously satisfy all performances of color tone, odor, and stability. Therefore, the appearance of colorless and stable rosin has been earnestly desired.

By the way, Japanese Unexamined Patent Publication No. 64-85265 discloses a method for producing a rosin that is colorless and has good stability. However, this method requires a hydrogenation step, so that a high pressure resistant reactor is used. However, there is a disadvantage in that the manufacturing cost is significantly increased due to the use of hydrogen and consuming a large amount of hydrogen.

[0007]

In view of the above-mentioned circumstances, the present inventor has proposed a novel production method capable of providing a rosin having further improved color tone, odor and stability performance of the conventionally known rosin at a low price. Aimed to develop.

[0008]

In view of the above-mentioned problems, the inventors of the present invention have investigated the raw material rosin species, refining operation, disproportionation, dehydrogenation,
As a result of intensive research to improve the various performances by paying attention to various conditions such as an antioxidant, the use of a specific raw material rosin, further by passing through a specific reaction step and preparation step, the above problems In order to solve the above-mentioned problems, a new production method capable of obtaining rosin having excellent performances which meets the object of the present invention was found.

That is, according to the present invention, a method for producing a colorless rosin characterized in that a disproportionation and a dehydrogenation reaction are simultaneously carried out in the presence of a catalyst with a purified rosin, and then an organic phosphorus compound is added to the reaction system. Pertain to.

In the present invention, an organic phosphorus compound having various functions such as decomposition of peroxide, prevention of oxidation and prevention of coloration is present in the reaction system after the raw material refined rosin is disproportionated and dehydrogenated. By doing so, the present invention relates to a novel production method capable of providing a rosin that has an almost colorless appearance and is excellent in odor and stability during heating. The rosin obtained by the method is completely unthinkable from the fixed idea formed by the various properties of conventional rosins. That is, according to the present invention, an almost colorless rosin is obtained, which eliminates the stereotypical idea that the appearance of rosin is conventionally yellow to yellowish brown. Moreover, the rosin retains the characteristics of conventional rosins, that is, the broad compatibility with various polymers.

By the way, the cause of coloration of rosin compounds is
The presence of a high molecular weight substance and an unsaponifiable substance contained in the raw material rosin, and the presence of a resin acid having a large oxygen absorption property such as abietic acid having a conjugated double bond in the resin acid. Seem. Therefore, the present invention has been completed focusing on the removal of the above-mentioned causes, and in the present invention, (1) using purified rosin as a raw material rosin, (2) disproportionating and dehydrating the purified rosin. It is indispensable to carry out an oxidization reaction, and (3) after the reaction, to add an organic phosphorus compound capable of functioning as a peroxide decomposer or an antioxidant to the reaction system.

Therefore, when the purified rosin is only disproportionated and dehydrogenated, when the unpurified rosin is disproportionated and dehydrogenated and then an organic phosphorus compound is added, or when the unpurified rosin is disproportionated and dehydrogenated In the case of purifying after dehydrogenation, it is impossible to obtain rosin having the various excellent properties which are the objects of the present invention.

The purified rosin which is the starting material of the present invention is
It refers to a purified product of gum rosin, wood rosin, tall oil rosin, which contains resin acids such as abietic acid, parastolic acid, neoabietic acid, pimaric acid, isopimaric acid, and dehydroabietic acid as the main components.

In the present specification, the term "purified" means to remove a high molecular weight substance which is considered to be generated from a peroxide contained in an unpurified raw material rosin and an unsaponifiable substance originally contained in the rosin. means. Specifically, operations such as distillation, recrystallization, and extraction may be performed, and purification by distillation is industrially preferable. If using distillation, usually temperature 2
It is appropriately selected from the range of 00 to 300 ° C. and the pressure of 1 to 10 mmHg in consideration of the distillation time. Recrystallization can be performed, for example, by dissolving unpurified rosin in a good solvent, distilling off the solvent to form a concentrated solution, and adding a poor solvent to this solution. Examples of good solvents include ketones such as benzene, toluene, xylene, chloroform, lower alcohols, and acetone, and acetic acid esters such as ethyl acetate, and examples of poor solvents include n-hexane and n-hexane.
Heptane, cyclohexane, isooctane and the like can be mentioned. Further, in the above-mentioned purification, an unpurified raw material rosin is made into an alkaline aqueous solution using alkaline water, an insoluble unsaponifiable matter is extracted with an organic solvent, and then an aqueous layer is neutralized to obtain a purified raw material rosin.

The present invention requires that the purified rosin be subjected to disproportionation and dehydrogenation reactions. The reaction conditions are not particularly limited and usual conditions can be adopted. For example, the presence of a purified rosin catalyst, less than ² hydrogen initial pressure is 10 Kg / cm in a closed vessel, preferably less than 5Kg / cm ^2, the reaction temperature is 100 to 300 ° C., preferably 200 to
It may be heated in the range of 280 ° C. Hydrogen is essentially unnecessary because it is a disproportionation and dehydrogenation reaction, but the initial hydrogen pressure is less than 10 kg / cm ² from the intention of utilizing the produced hydrogen for the reduction of peroxide as described above. The pressure may be adjusted by the self-pressure of the produced hydrogen or by slightly supplying hydrogen from the outside. Various known catalysts can be used without particular limitation as the above-mentioned catalyst, but palladium-based, rhodium-based, and platinum-based catalysts are preferable. The catalyst is usually used by supporting it on a carrier such as silica or carbon. The amount of the catalyst used is usually about 0.01-5% by weight, preferably 0.05-
It is set to 3% by weight.

The resin acid composition of the rosin obtained by the above method is slightly changed depending on the hydrogen supply pressure, but usually 15 to 35% by weight of dihydro compound and 85 to 65 of dehydroabietic acid are used.
It becomes weight%. The peroxide value of the obtained rosin is usually 1 or less.

In the present invention, it is essential to add the organophosphorus compound after the above steps are completed. This further improves color tone and stability. The organophosphorus compound has the following general formula:

[0018]

[Chemical 1]

(In the formula, R is the same or different and is an alkyl group having 1 to 12 carbon atoms, a phenyl group, or 1 to 12 carbon atoms.
Various groups represented by at least one selected from the group consisting of an alkylphenyl group having an alkyl group and a dialkylphenyl group having two alkyl groups having 1 to 12 carbon atoms are listed.

Specific examples include triphenyl phosphite, tricresyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite,
4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite,
Tris (dinonylphenyl) phosphite, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-
Examples thereof include oxa-10-phosphaphenanthrene. Among the above, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, in consideration of lightening effect, stabilizing effect, and cost.
Various phosphite compounds such as tris (dinonylphenyl) phosphite are preferred.

The amount of the organic phosphorus compound used is 1.0% by weight or less, preferably 0.5% by weight or less, based on the raw material-purified rosin. If it is less than 0.01%, a sufficient improvement effect cannot be obtained, and if it exceeds 1.0% by weight, it is meaningless to use it in excess and it becomes uneconomical.

The method of adding the organophosphorus compound is not particularly limited as long as it is added to the reaction system after the completion of the reaction, but usually, after the reaction is completed, the pressure is returned to normal pressure and then as quickly as possible. It is preferable, and it is more preferable to add it in an atmosphere without oxygen. Further, the temperature of the reaction system at the time of adding the organophosphorus compound is not particularly limited, but may be at or below the decomposition temperature of the organophosphorus compound, usually 27
It is set to 5 ° C or lower. It should be noted that the presence of the organophosphorus compound during the reaction is not preferable because it inhibits the progress of the dehydrogenation reaction and reduces the color tone of the resulting rosin.

The final target product, rosin, obtained by the method of the present invention has a color tone that is almost colorless in appearance.
Moreover, it is excellent in various properties such as odor, stability and compatibility upon heating. Therefore, not only can it be suitably used as a modifier for a soap-based detergent composition, but also the alkali metal salt of rosin can be suitably used as a synthetic rubber and an emulsifier for emulsion polymerization. By introducing the rosin into an esterified product, tackifiers for hot melt adhesives, modifiers for rubbers and various plastics, raw materials for traffic paints, chewing gum base materials, modifiers for inks / paints, pigments It can be suitably used as a coating agent, solder flux, etc., and can improve the commercial value of the final product in these applications.

[0024]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a rosin having a significantly improved performance such as color tone, odor and stability as compared with a conventionally known rosin at a relatively low cost.

[0025]

EXAMPLES The method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these.

Example 1 (1) Purification Acid number 172, softening point 75 ° C, unpurified Chinese gum rosin with color tone Gardner 6 was distilled under a nitrogen blanket under reduced pressure of 3 mmHg to give acid value 175.2 and softening point 80. The main distillate having a general constant of color Gardner 4 at 0.0 ° C. was the purified rosin.

[0027]

[Table 1]

(2) Disproportionation and dehydrogenation reaction 200 g of the purified rosin and 0.6 g of 5% palladium carbon (water content 50%) were charged into a 1 liter shaking autoclave to remove oxygen in the system. , The system was pressurized with hydrogen to 0.5 Kg / cm ² and heated to 275 ° C., and disproportionation and dehydrogenation reaction were simultaneously carried out at the same temperature for 3 hours to give an acid value of 171.3 and a softening point of 85. A rosin having a color tone of Gardner 2 was obtained at 5 ° C.

(3) Addition of organophosphorus compound 0.1 g of triphenylphosphite was added to 100 g of the rosin.
g, and after stirring at about 200 ° C. for 30 minutes, the system is cooled to room temperature, the acid value is 171.2 and the softening point is 85.0.
A rosin having a color tone of Hazen 120 was obtained.

Examples 2 to 3 In Example 1, the type of the organophosphorus compound was sequentially replaced with tris (nonylphenyl) phosphite and diphenylisodecylphosphite, and the amount of each was 0.2 g. Others were done in the same manner, and each rosin was obtained. The product of Example 2 has an acid value of 170.7 and a softening point of 84.
The color tone was Hazen 150 at 5 ° C. In Example 3, the acid value was 171.1, the softening point was 84.5 ° C., and the color Hazen was 150.

Comparative Example 1 Acid number 172 was used as the raw material rosin, the reaction was carried out under the same conditions as (2) of Example 1 except that unpurified Chinese gum rosin with a softening point of 75 ° C. and color tone Gardner 6 was used. 16
A rosin of 7.3, softening point 84 ° C. and color tone Gardner 5 was obtained.

Comparative Example 2 The rosin obtained in Example 1 (2) was used.

The methods for measuring various performances are as follows. The results are shown in Tables 2 and 3. (Peroxide value) Based on the Japan Oil and Fat Chemistry Association standard oil and fat analysis test method (2.4 / 12-86). (Resin Acid Composition in Rosin) Each rosin before and after the disproportionation and dehydrogenation reaction was subjected to gas chromatography measurement according to ASTM D3008-82. (Heating stability) 10 g of the sample was placed in a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and the sample was left standing in a circulating air dryer at 200 ° C. without a lid, and changes in color tone (Gardner) with time were observed. (Weather resistance) 2.0 g of resin having a uniform particle size of 60 to 100 mesh was placed in an ointment can having an inner diameter of 5.6 cm and a height of 1 cm, and the weight increase when a 400 W mercury lamp was irradiated from a distance of 40 cm for 15 hours (oxygen absorption The amount and the color tone (gardner) were observed. The color tone is based on evaluation in a 50% toluene solution.

[0034]

[Table 2]

[0035]

[Table 3]

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[Procedure amendment]

[Submission date] September 4, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

The present invention requires that the purified rosin be subjected to disproportionation and dehydrogenation reactions. The reaction conditions are not particularly limited and ordinary conditions can be adopted. For example, the presence of a purified rosin catalyst, less than ² hydrogen initial pressure is 10 Kg / cm in a closed vessel, preferably less than 5Kg / cm ^2, the reaction temperature is 100 to 300 ° C., preferably 200 to
It may be heated in the range of 280 ° C. Hydrogen is essentially unnecessary because it is a disproportionation and dehydrogenation reaction, but the initial hydrogen pressure is less than 10 Kg / cm ^{2 in} order to utilize the produced hydrogen for the reduction of peroxide as described above. The pressure may be adjusted by the self-pressure of the produced hydrogen or by slightly supplying hydrogen from the outside. As the above-mentioned catalyst, various known catalysts can be used without particular limitation, but palladium-based, rhodium-based and platinum-based catalysts can be preferably exemplified. The catalyst is usually used by supporting it on a carrier such as silica or carbon. The amount of the catalyst used is usually 0.01 to 5% by weight, preferably 0.05 to 5% by weight, based on rosin.
It is set to 3% by weight. In addition, in the dehydrogenation reaction, a solvent such as an alicyclic hydrocarbon such as cyclohexanone or decalin or an aromatic hydrocarbon such as toluene or xylene can be appropriately used.

[Procedure amendment]

[Submission date] September 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

The present invention requires that the purified rosin be subjected to disproportionation and dehydrogenation reactions. The reaction conditions are not particularly limited and ordinary conditions can be adopted. For example, the presence of a purified rosin catalyst, less than ² hydrogen initial pressure is 10 Kg / cm in a closed vessel, preferably less than 5Kg / cm ^2, the reaction temperature is 100 to 300 ° C., preferably 200 to
It may be heated in the range of 280 ° C. Hydrogen is essentially unnecessary because it is a disproportionation and dehydrogenation reaction, but the initial hydrogen pressure is less than 10 Kg / cm ^{2 in} order to utilize the produced hydrogen for the reduction of peroxide as described above. The pressure may be adjusted by the self-pressure of the produced hydrogen or by slightly supplying hydrogen from the outside. As the above-mentioned catalyst, various known catalysts can be used without particular limitation, but palladium-based, rhodium-based and platinum-based catalysts can be preferably exemplified. The catalyst is usually used by supporting it on a carrier such as silica or carbon. The amount of the catalyst used is usually about 0.01-5% by weight, preferably 0.05-
It is set to 3% by weight. In addition, in the dehydrogenation reaction, a solvent such as an alicyclic hydrocarbon such as cyclohexane or decalin or an aromatic hydrocarbon such as toluene or xylene can be appropriately used.

Claims (6)

[Claims] 1. A process for producing a colorless rosin, which comprises performing a disproportionation and a dehydrogenation reaction on a purified rosin at the same time in the presence of a catalyst, and then adding an organic phosphorus compound to the reaction system. 2. The method according to claim 1, wherein the catalyst is a palladium, rhodium or platinum-based catalyst. 3. The reaction pressure is 10 kg in the reaction.
The method according to claim 1, which is less than / cm ² . 4. The method according to claim 1, wherein the resin acid composition of the rosin after the reaction is 15 to 35% by weight of dihydro compound and 85 to 65% by weight of dehydroabietic acid. 5. The method according to claim 1, wherein the amount of the organic phosphorus compound added is 0.01 to 1.0% by weight based on the raw material-purified rosin. 6. The organic phosphorus compound is represented by the following general formula: (In the formula, R is the same or different and has two alkyl groups having 1 to 12 carbon atoms, a phenyl group, an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms and two alkyl groups having 1 to 12 carbon atoms. The method according to claim 1 or 2, which is at least one selected from the group consisting of dialkylphenyl groups.