JPS60255868A - Esterification for rosin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to a novel process for the preparation of pentaerythritol esters of rosin. In particular, the present invention is characterized by reducing the reaction time for the production of rosin/pentaerythritol ester by reacting rosin with pentaerythritol in the presence of a trace amount of phosphine 1ft(1-(3PO2) as a catalyst). It is to do.Also,
When tall oil rosin is esterified, the rosin/
The color properties of pentaerythritol are also improved.

Description of the Prior Art Rosin is a monocarboxylic acid mixture having primarily fused rings of 20 carbon atoms (C2o). This monocarboxylic acid is typified by levopimaric acid and abietic acid, which form various substituents. The rosins used in this invention are rubbery rosin, wood rosin and 1-l oil rosin.

The hydrophilic components contained in the liquid part from tree sap and wood formation layer become hydrophobic solid components by natural separation or conversion, but in general, various rubbery substances, 11 resins, etc. and wax is formed. The oleoresin intermediate in this method is made from southern yellow pine (5 out
This is typified by the vine rubber that flows out from the cut end of the trunk of the hern yellowpine tree. Vine gum contains about 80% rosin and about 20% turpentine.

Resinification from oleoresins occurs by natural evaporation of oil from the extrudate or by slowing down the white and red materials in ducts. Pine trunks are useful for cutting, chipping, extraction with hexane or high-boiling paraffin, and fractional distillation to produce wood rosin, wood turpentine, and turpentine compounds. In the Kraft process, the Ia-acid pulping process in papermaking, pine is digested with alkali producing crude tall oil and crude turpentine sulfates as by-products. Fractional distillation of crude tall oil produces tall oil rosin and fatty acids.

The chemical transformation of rubbery rosin, wood rosin and tall oil rosin is esterification in the process of this invention. Since the products obtained by esterification of rosin were found to have useful properties, a number of esterification methods, especially with polyhydric alcohols, were developed. US Patent No. 2,369,125, No. 2,5
90,910JL15 J: Hi No. 2, 572.086
@ discloses a method for esterifying rosin with glycerol and pentaerythritol in the presence of a polyhydric alcohol.

In this case, the esterification is usually carried out prior to the disproportionation treatment of the rosin.

As is well known, the disadvantage of esterifying tall oil rosin with penta-1 litritol is that there are problems with angular changes compared to esterification with glycerol. When tall oil 0 gin with a Gardner color number of 8 is used as a starting material, the color number of the pentaerythritol ester is 13 to 18, while the color number of the glycerol ester is 8 to 9. Also,
The time required for ester formation is also long; the formation time for tall oil rosin/glycerol ester is 10 to 12 hours, whereas the formation time for tall oil rosin/pentaerythritol ester under the same conditions is 30 to 48 hours.
It takes time too.

U.S. Patent Nos. 3,780,012 and 3.780.
No. 013 shows that pentaerythritol esters formed using tall oil rosin are significantly darker in color than when rubbery or wood rosin is used. In U.S. Pat. No. 3,780,012, the rosin is treated with paraformaldehyde and then distilled prior to ]-tellification. In US Pat. No. 3,780,013, a phenol sulfide compound is added during esterification. The color of the product obtained by such a method is M on the U, S, D, A scale (corresponding to 11 to 12 on the Gardner color number).
It is. Also, a 20% excess amount of pentaerythritol is used in this example.

In US Pat. No. 2,729,660 it is shown that strong acids, etc. used as catalysts during esterification darken the color of the product. In this patent, 0.5% to 5% of aliphatic ester or aromatic ester of phosphorous acid is added as an esterification catalyst for higher fatty acids, rosin acids, or mixtures thereof. In addition to preventing the color of the product from becoming light during esterification, attention has also been paid to shortening the reaction time. An inherent drawback of this method is that during the esterification step, the alcohol used to form the sacrophosphoric ester catalyst decomposes and produces a malodor.

U.S. Pat. No. 4,172,070 shortens the esterification time of tall oil rosin with pentaerythritol and stabilizes it against oxygen by using allyl sulfonic acid in place of conventional esterification catalysts such as calcium oxide. A method is disclosed for producing rosin esters having excellent properties and improved color and softening point. However, since this method uses a large amount of pentaerythritol (35% excess), the amount of pentaerythritol is significantly reduced.

The ring and ball softening point of this product is 77°C to 86.5°C. Note that the softening point of commercially available pentaerythritol ester is 95°C to 105°C.

OBJECTS OF THE INVENTION It is an object of this invention to provide a new process for the preparation of pentaerythritol esters of rosin.

Another object of this invention is to use a catalyst to accelerate the rosin/pentaerythritol reaction and to shorten the reaction time.

Another object of the present invention is to reduce m of the pentaerythritol used, thereby lowering manufacturing costs and lowering the softening point i (preferably from 95°C to 105°C).

Yet another object of this invention is to provide a method for preparing pentaerythritol esters having a color comparable to that of glycerol esters of tall oil rosin.

SUMMARY OF THE INVENTION It has been found that when phosphinic acid (also called hypophosphorous acid) is used as a catalyst, it acts effectively even in trace amounts to promote the reaction between rosin and pentaerythritol. In particular, when tall oil rosin is reacted with at least an equal amount of pentaerythritol, 0.05% to 0.5% phosphinic acid is added by weight to rosin and the reaction is carried out at about 180°C to about 300°C. When reacted at high temperature, the Gardner color number of the tall oil rosin ester produced is only 0 to 2 higher than the Gardner color number of the raw rosin.

DESCRIPTION OF EXAMPLES Phosphinic acids are strong reducing agents and are useful for light-colored fatty acids (U.S. Pat. No. 3,232,968), poly(oxyalkylenes),
Carboxylic acid esters with compounds (U.S. Pat. No. 979
．． 673 and U.S. Pat. No. 3.071.6011), acrylic and methacrylic esters of glycols (Japanese Patent No. 7311084@) or light-colored alkyl resins (Japanese Patent No. 12997). Or used as a bleaching agent. Phosphinic acid is also used as a treatment agent for tall oil. In this case, impurities and pigments contained in tall oil (
The phosphinic acid converts color bodies into non-distillable compounds, promoting the decarboxylation of the rosin acids they contain (U.S. Pat. No. 2,444).
1.197@).

In the novel rosin esterification process currently in use, a small amount of phosphinic acid is used as the only esterification catalyst.

The rubbery rosin, wood rosin, and tall oil rosin that are the targets of the method of this invention may be subjected to another treatment prior to esterification. For example, in addition to the distillation treatment performed in the fractional extraction method, disproportionation, hydrogenation, polymerization,
Alternatively, processing that is a combination of these processes can be performed as IM.

Generally, esterification of rosin involves introducing the rosin into a reaction vessel, adding up to 18% excess pentaerythritol in its IM ratio relative to 0 gin, and 0.01% to 0.5% rosin.
% of phosphinic acid.

The reaction temperature is about 180°C to 300°C, with a preferred temperature range of about 250°C to 280°C. Also,
Reaction time [approximately 25 hours or when the acid value of the rosin is approximately 15
Until the following. The preferred addition base of small sphinic acids as a catalyst is from about 0.1% to about 0.25% by weight relative to the rosin; addition of more than 0.5% of this phosphinic acid has no effect.

The esterification reaction is preferably carried out in an inert atmosphere. This can be accomplished by venting the nitrogen in the reaction vessel before addition of the reactants and introducing nitrogen during the reaction. A characteristic of rosin ester is that it is light in color, but its color is easily affected by oxygen gas, so it is necessary to minimize contact with oxygen as much as possible.

Also, the advantage of phosphinic acid catalysts is that the discoloration effect during the esterification reaction is small. Therefore, the color of the rosin ester does not differ much from the color of the rosin used as a raw material. When tall oil rosin is esterified, the color of the resulting ester becomes darker due to the action of the catalyst used in the method of this invention, but the extent of this darkening is only slightly to 0
or 2. Therefore, when tall oil rosin with a Gardner color number of 5 is used as a raw material, the Gardner color number of the produced ester is 5 to 7, and the Gardner color number is 1.
If zero tall oil rosin is used, the resulting ester will have a Gardner color number of 10 to 12.

In a preferred embodiment of the process of the present invention, the starting material rosin is exposed to an inert atmosphere in a reaction vessel, and then the rosin has a flfi ratio of 0.02% phosphinic acid and an active small sulfinic acid equivalent of 50%. aqueous solution) and 15% to 18% excess pentaerythritol. Once the mixture is heated to 275° C., an inert gas such as nitrogen is slowly blown in. Note that this temperature is maintained for the total reaction time (18 to 24 hours). When about 18 hours to 20 o'clock have passed after the start of the reaction, the inert gas atomization was switched to the steam atomization, and solid sodium hydroxide was added at an ff1ffi ratio of about 0.053% to the rosin to neutralize the phosphinic acid catalyst. Cover and further cool the resulting mixture.

(Note that a 50% aqueous solution of sodium hydroxide may be used, but in that case it must be added prior to steam spraying.) In a more preferred embodiment, the rosin used is tall oil. rosin, and upon cooling, the Gardner color number change of the final product with respect to the raw material rosin is 0 to 2, and its balls and rings (B
All and Ring) The softening point is about 95°C to about 105°C.

Next, the examples show that the rosin-pentaerythritol ester prepared by the method of the present invention exhibits unexpected color change properties.

It can also be seen that the required reaction time is short.

In the following examples, unless otherwise specified, ratios are expressed by weight.

Example 1 In a suitable reaction vessel, tall oil D with Gardner color number 10 was added.
100 parts of gin, 115 parts of pentaerythritol and 5
Add 0.2 parts of 0% active phosphinic acid aqueous solution. The mixture thus obtained was heated to 250°C to 260°C and maintained for 20 hours, resulting in an acid value of 13. An ester with a ring and ball softening point of 97° C. and a Gardner color number of 11 is obtained.

Example 2 When a tall oil rosin with a Ga-donor color number of 5 was used and the other conditions were the same as in Example 1, the reaction was carried out, resulting in an acid value of 15. An ester with a softening point of 96° C. and a Gardner color number of 6+ is obtained.

Example 3 When the reaction is carried out under the same conditions as in Example 1 without adding phosphinic acid, it takes 45 hours to reach an acid value of 12, and the final Gardner color number is 18+. As can be seen by comparing the first and second examples, the reaction in this example demonstrates that the phosphinic acid has catalytic activity.

Example 4 Into a suitable reaction vessel, 100 parts of tall oil rosin with Gardner color number 6 and 12.3 parts of pentaerythritol were charged, and in place of bosphinic acid, 100% active calcium hydroxide (used as a catalyst) was added. U.S. Patent No. 3.780
．． 013) is added in an amount of 0.1% by weight. The mixture thus obtained was heated to 270°C and held for 24 hours, resulting in an acid value of 5° and a ball softening point of 10.
An ester with a temperature of 2° C. and a Gardner color number of 13 is obtained.

As can be seen by comparing the first and second examples, this example demonstrates that the catalytic effect of bosphinic acid is superior to common esterification catalysts.

Example 5 When the reaction was carried out without using a catalyst and under the same conditions as in Example 4, the acid value was 10. An ester with a softening point of 99° C. and a Gardner color number of 12 is obtained.

In this case, the required holding time at the reaction temperature is 24
It's time.

Example 6 100 parts Gardner color 7+ tall oil rosin in a suitable scale esterification reaction plant.

Charge 122 parts of pentaerythritol and 0.2 parts of 50% active phosphinic acid aqueous solution. Add this mixture to 280
C. and held for 17.5 hours, yielding an ester with an acid number of 89, a ring and ball softening point of 96.degree. C., and a Gardner color number of 8.

Example 7 In a suitable reaction vessel, commercially available partially hydrogenated wood rosin (Gardner color number 5+>100 parts, Penn erythritol 12.3 parts and 50% active bosphinic acid aqueous solution 0.2
Input the department. This mixture was heated to 270°C and held at that temperature for 17.5 hours, resulting in an acid value of 14. An ester is obtained with a ring and ball softening point of 94° C. and a Gardner color number of 6.5.

Example 8 When a hydrogenated tall oil rosin with a Gardner color number of 4+ was used and the other conditions were the same as in Example 7, the reaction was carried out with an acid value of 14. An ester with a softening point of 93° C. and a Gardner color number of 8+ is obtained. In this case, the required holding time at the reaction temperature is 175 hours.

Example 9 Disproportionated tall oil rosin with guard boo color number 4+ was used and the upper limit temperature was 250°C, other conditions were as in Example 7.
When the reaction is carried out at the same temperature as the acid value, the acid value is 12. Softening point 90℃
and an ester with a Gardner color number of 65 is obtained. In this case, the required holding time at the reaction temperature is 39 hours.

Example 10 In a suitable reaction vessel, 100 parts of Gardner color number 10 gummy rosin, 11.5 parts of pentaerythritol, and 5
Add 02 parts of 0% active phosphinic acid aqueous solution. When this mixture is heated to 270°C and held for 16 hours, the acid value is 1.
2. An ester is obtained with a ring and ball softening point of 1025 DEG C. and a Gardner color number of 8-.

Example 11 Using the method of this invention, pentaerythritol esters are obtained from a disproportionated and distilled tall oil rosin sample. One rosin sample was prepared by adding 0.2% of bosphinic acid catalyst after distillation and before cooling (while the sample was hot), and stirring this at 177° C. for 30 minutes before cooling. Note that the Gardner color number of both samples is 2-. The results are shown in the table.

(continued on next page) 5559-7B 12.3 97 6- c5559-
8^c12.396 12 dlo, 4 96 7.
5 e a, All esters were prepared with an upper limit temperature of 260'Cr, C containing 0.2% phosphinic acid, 0.5% phosphinic acid added d, no catalyst added e, 0.3% phosphinic acid added Esters prepared from rosins pre-containing 0.2% catalyst are generally inferior in color to esters prepared with subsequent addition of catalyst. Even if 0.3% of catalyst is added later, the product is darker.

Example 7. a; 9.10.11 demonstrates the catalytic activity of phosphinic acids for the esterification of rosins other than tall oil rosins and pretreated rosins.

Although the present invention has been described above based on various embodiments, the present invention is not limited to the above-mentioned embodiments, and can be implemented with various changes according to those skilled in the art.

Applicant Wesdopa] - Boreshin Agent Patent attorney Hidehiko Okada (2 others)

Claims (16)

[Claims] (1) A method for esterifying rosin with at least an equal amount of pentaerythritol, wherein the esterification reaction is carried out by heating the rosin and pentaerythritol in the presence of a phosphinic acid catalyst. . (2) the small sulfinic acid is contained in an amount of 0.001% to 0.05%, and the reaction is carried out in an inert atmosphere;
The reaction temperature and reaction time are 180°C to 300°C and 18 to 20 hours, respectively, and after the reaction is completed, steam is sprayed and sodium hydroxide capable of neutralizing phosphinic acid is added. A method for esterifying rosin according to claim 1. (3) The rosin is 1 at 250°C to 280°C.
Claim 1 characterized in that it is esterified with a 5% to 18% excess of pentaerythritol.
The rosin esterification method described in Section 1. (4) The rosin according to any one of claims 1, 2, or 3, characterized in that the rosin is 1-oil rosin, rubbery rosin, or wood rosin. Esterification method. (5) The method for esterifying rosin according to claim 4, wherein the rosin is a disproportionated rosin, a hydrogenated rosin, or a polymerized rosin. (6) The Gardner color number of the tall oil rosin ester is O to 2 larger than the Gardner color number of the tall oil rosin, and the ball and ring softening points of the ester are 95.
5. The method for esterifying rosin according to claim 4, wherein the temperature is 105°C to 105°C. (7) In the method for sprucing rosin with pentaerythritol, the esterification reaction is carried out in an inert atmosphere in the presence of 0.001% to 0.5% liphosphinic acid based on the weight ratio of the rosin, and the reaction temperature and The time is about 180℃ to about 300℃ and Jl high 2, respectively.
A method for esterifying rosin, characterized in that the time is 0 hours, and the phosphinic acid is neutralized with sodium hydroxide. (8) The rosin is esterified with a 15% to 18% excess of pentaerythritol in the presence of 0.1% to 0.25% phosphinic acid, and the reaction proceeds under atomization of inert gas. 8. The method for esterifying rosin according to claim 7. (9) The method for esterifying rosin according to claim 7, wherein the esterification reaction is carried out at 250°C to 280°C. (10) The rosin esterification method according to claim 7, wherein the gas constituting the inert atmosphere is nitrogen gas. (11) The method for esterifying rosin according to claim 7, 8 or 9, wherein the rosin is tall oil rosin, rubbery rosin or wood rosin. (12) The rosin esterification method according to claim 10, wherein the rosin is a disproportionated rosin, a hydrogenated rosin, or a polymerized rosin. (13) The Gardner color number of the tall oil rosin ester is O to 2 larger than the Gardner color number of the tall oil rosin, and the ball and ring softening points of the ester are 9.
The method for esterifying rosin according to claim 11, characterized in that the temperature is 5°C to 105°C. (14) A method for esterifying tall oil rosin, comprising:
In the temperature range of 80° C. to 300° C., in the presence of bosphinic acid of 0.01% to 0.5% by weight relative to the tall oil rosin, the tall oil rosin is Tall oil rosin produced by reacting with 818% excess amount of pentaerythritol/
The Gardner color number of the Benkyu erythritol ester is 0 to 2 larger than the Gardner color number of the tall oil rosin, and the ball and ring softening points of the ester are 95.
A method for esterifying tall oil rosin at a temperature of 105°C to 105°C. (15) The phosphinic acid present is between 0.1% and 0.025%.
%, and the reaction proceeds under spraying of an inert gas. 15. The method for esterifying tall oil rosin according to claim 14. (16) The method for esterifying tall oil rosin according to claim 14, wherein the reaction temperature is 250°C to 280°C.