JPS6081269A - Production of rosin ester - Google Patents

Abstract

PURPOSE:To obtain a light-colored rosin ester having good stability to oxidation and coloring by heat, by esterifying a distilled rosin with an alcohol in the presence of a metal disproportionation catalyst for the rosin. CONSTITUTION:(A) A rosin, preferably gum rosin (usually obtained by vacuum simple distillation under <=50mm.Hg pressure at 200-300 deg.C internal temperature of a still) is esterified with (B) an alcohol, e.g. n-octyl alcohol, in the presence of (C) an esterification catalyst, (D) preferably palladium-carbon as a metal disproportionation catalyst for the rosin and if encessary (E) a phenolic antioxidant, etc. to afford the aimed rosin ester. Preferably, the component (D) in an amount of 0.01-0.1wt% based on the component (A) is added to the component (A) 1- 5hr before the completion of the reaction. USE:Pressure-sensitive adhesives, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a rosin ester that is light in color and has good stability against heat coloring.

Nisdell rosin is one of a group of resins called hard resins, and is used industrially as a raw material for adhesives, pressure-sensitive adhesives, ink resins, traffic paints, heat-sealable plastics, etc. Widely used.

Esterified products of rosin are usually yellow or tan colored, have J'3, and are poor in heat resistance and aging resistance. Therefore, in these industries, a rosin ester is desired which has physical properties (cloudiness, light color, resistance to oxidation and heat discoloration, and good carbon stability).

Esters of disproportionated rosin or hydrogenated rosin are known as [-1 gin esters, which have improved stability against oxidation and heat discoloration. Due to esterification, these rosins not only developed six colors during the soil sprue formation reaction, but also had insufficient stability against oxidation and heat coloring.

JP-A-55-9605 discloses a method for producing a highly stable rosin Nisdel, which uses a rosin compound thought to be produced from peroxides contained in the raw material rosin by distilling a disproportionated rosin, and After removing the unsaponifiables originally present in the raw material rosin and the unsaponifiables generated during the disproportionation reaction, this steamed rosin is removed. A method of esterifying purified disproportionated rosin with alcohol is described, but in this method, a coloring phenomenon occurs during the esterification reaction of -C, resulting in oxidation of the resulting rosin ester. However, the stability of heat coloring was not satisfactory.

In addition, this method requires three steps: a disproportionation reaction step, a hot surface one culm step, and an esterification reaction step, so it has some disadvantages from a practical standpoint.

The Ministry of the Invention and others investigated the cause of seven colors occurring in the rosin ester doo and found the following facts. (1) The six colors of rosin ester are due to the high molecular weight substances in rosin.

(2) Even if the high molecular weight substances are removed by distilling the rosin, the color component of the heated resin is not completely removed and becomes colored during the subsequent Nisdellization reaction.

(3) The cause of poor aging resistance of rosin esters is due to small polymeric substances in rosin, such as resin acids having abietic acid type conjugated double bonds.

(4) The esterification reaction and disproportionation reaction of rosin proceed at the same temperature.

Based on the above facts, as a result of further investigation, we decided to esterify the heated rosin with alcohol in the presence of a rosin disproportionation catalyst.1. and esterification reaction are li, jl 11. In 1997, it was discovered that a 1'' synester, which was extremely pale in color and stable against heat and lS2 molecules, could be obtained. The present invention is characterized in that the heated rosin is subjected to an esterification reaction with an alcohol in the presence of a metal disproportionation catalyst.

The rosins used in the present invention include camrosin, wood rosin, and tall oil rosin, which are mainly composed of resin acids such as abidic acid, balasmy phosphoric acid, ne-A abiedic acid, pimaric acid, isobimaric acid, and dehydroabietic acid. etc., and use one that has been heated.

The hot surface of rosin is usually 20 mmHg or less at a pressure of
It is carried out at an internal temperature of 0 to 300℃, and methods such as vacuum single heating surface, vacuum steam heating, thin film vacuum heating oil, etc. are adopted. Under normal heating and temperature conditions, 2 to 10% of polymer suspended materials , the remaining pitch is removed. Furthermore, when obtaining rosin Nisdel with a high softening point, it is preferable to also remove about 2 to 10% of the initial fraction.

Alcohols include monohydric alcohols such as n-ocdyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, and stearyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and neopentyl. Dihydric alcohols such as glycols, glycerin,
trihydric alcohols such as trimethylolpropane; tetrahydric alcohols such as pentaerythritol and diglycerin;
J of dipentaerythritol: Hexahydric alcohol and the like.

The esterification reaction can be carried out by a known method, that is, by heating the rosin and alcohol at a temperature of 1 bO to 300° C. in the presence of an inert gas, and removing the reaction product water from the system. As a catalyst for the Nisderization reaction, known catalysts such as acetic acid, para-1-toluenesulfonic acid, phosphoric acid, lithium hydroxide, calcium hydroxide, magnesium oxide, zinc oxide, and calcium acetate can be used.

Catalysts for the disproportionation reaction of rosin include: iron iodide, sulfur, sulfur dioxide, selenium, nickel-carbon,
Ruthenium-carbon, palladium-carbon, platinum-
If iodine or iron iodide is used, the color of the rosin ester will be intense, and sulfur,
When sulfur compounds such as sulfur dioxide are used, the odor during production is intense, and the odor of the resulting rosin ester is also intense. Furthermore, selenium is highly toxic and undesirable. In the water spraying invention, a metal disproportionation catalyst is used.

Examples of the metal disproportionation catalyst for rosin used in the present invention include platinum-nocophone, nickel-carbon, ruthenium-carbon, palladium-carbon, nickel formate, nickel chromate, and the like. however,
Nickel formate and nickel chromate lower the softening point of the resulting rosin ester, and nickel-based catalysts are not so preferred because they give the resulting rosin ester a bluish-green color. Palladium-carbon, ruthenium-carbon and O. platinum-carbon have a good color tone of the rosin ester when heated, good stability under heat, and a high softening point. Therefore, it is particularly preferable.

The addition H1 of the rosin disproportionation catalyst is preferably 0.005 to 1% to the hot rosin, and the color tone of the Ll synester,
From the viewpoint of stability against heat and oxygen and economic efficiency, 0.
Addition of 0.01 to 0.1% is appropriate.

The rosin disproportionation catalyst should be mixed together during the rosin esterification reaction. If a disproportionation catalyst is added in the early hours of the esterification reaction, the color tone of the resulting rosin ester will improve, but its stability against heat and oxygen will decrease, and if it is added before the esterification reaction, the resulting rosin ester will become less stable. The color tone of the ester becomes poor. Therefore, it is appropriate to add the rosin metal disproportionation catalyst 1 to 5 hours before the esterification reaction is completed.

The rosin ester obtained according to the present invention is extremely pale in color compared to conventional rosin esters, and is stable against oxidation and heat discoloration. Therefore, it can be used as a raw material for pressure-sensitive adhesives, adhesives, inks, rough paints, sealants, and heat-sealable plastics.

If a higher degree of stability is required for the rosin ester, it is also possible to use a phenolic antioxidant or a phosphorous gx ster stabilizer together.

Examples of the present invention will be described below.

I used a thermometer and an air cooling tube to check the temperature of the rosin 2! 1200 ml of rosin in a hanging distillation flask! After heating to 200℃ in a nitrogen stream and completely melting the rosin,
The system was then cooled to 3 mmHg, and the temperature inside the flask was raised to 120 to 280°C for distillation to obtain hot rosins Δ to D not shown in Table 1.

4;* Distillation temperature 230-270'C :l: =1= :l: Harima Kasei Kogyo Co., Ltd. Product name Banchiis G-100F Rosin Nisdel Synthesis Example 1 Stirrer, water drain pipe with cooler, hygrometer In a glass reaction vessel (200 CC volume) equipped with a nitrogen blowing tube, hot rosin A was added as a rosin, 10091 alcohol was added, glycerin was added as 11.69, and lithium hydroxide monohydrate was added as an esterification reaction catalyst at 0.0. 1! J, and 5% palladium-carbon as a disproportionation catalyst were added to 10111 (+ each), and the esterification reaction was carried out at 270°C for 8 hours with stirring at 270°C under a nitrogen atmosphere, and then cooled to 230°C. The catalyst was removed by filtration to obtain rosinnisdel.

Example 2 The palladium-carbon matrix as a disproportionation reaction catalyst is 5
A rosin ester was obtained in the same manner as in Example 1 except that the amount was 0 mg.

Example 3 Palladium-carbon suspension as a disproportionation reaction catalyst
A rosin ester was obtained in the same manner as in Example 1, except that the amount was 00 mg.

Example 4 Hot rosin A was added as rosin to the reaction vessel described in Example 1.
100! + and glycerin as alcohol 11.
60 each, prepared under nitrogen atmosphere 270'01''-
The esterification reaction was carried out with stirring, and after 2 hours, 50 mg of 5% palladium-carbon was added as a disproportionation catalyst, and the esterification reaction was carried out for a total of 8 hours. The catalyst was removed in the same manner as in Example 1, and the rosin An ester was obtained.

Example 5 Disproportionation reaction 191: Rosinnisdale was obtained in the same manner as in Example 4, except that palladium-carbon as Ka was added after 5 hours at 270'C.

Example 6 Palladium ~7J-hon as a disproportionation reaction catalyst was
At 70'C, rosin was added as in Example 4, except that it was added after 7 hours.

Example 7 A rosin ester was obtained in the same manner as in Example 5, except that 130 pentaerythritol was used as the alcohol instead of 11.6q of glycerin.

Example 8 A C rosin ester was obtained in the same manner as in Example 7, except that 100 g of thermotemperature rosin B was used as the rosin instead of thermotemperature rosin Δ.

Example 9 A rosin ester was obtained in the same manner as in Example 7, except that 100 f+ of hot rosin C was used in place of hot rosin A.

Practical Example 10 As a disproportionation catalyst, instead of palladium-carphone, 5
% Ruthenium-Carbon! The procedure was the same as in Example 7 except that J'CC rosin ester was used.

Example 11 As a disproportionation catalyst, instead of palladium-7J-phone,
Example 7 except that 50 m9 of 5% platinum-carbon was used.
In the same manner as above, "-C rosin" was obtained.

Example 12 As the alcohol, instead of pentaerythri 1 hel,
A rosin ester was obtained in the same manner as in Example 7, except that dotecyl alcohol was used.

Comparative Example 1 As 0 gin, instead of hot rosin A, disproportionated rosin D was used as 100! A rosin ester was obtained in the same manner as in Example 11, except that JJ was used and no disproportionation catalyst was added.

Comparative Example 2 As 0 gin, 100 ml of Nokomurosin from China, which is not distilled with C1, was substituted for prepacked rosin A. A rosin ester was obtained in the same manner as in Example 2, except that It was used and the Nisdell conversion catalyst was not used.

Comparative Example 3 As 0 gin, tall oil rosin 1009, which is not heated, was used instead of Chinese repulsion rosin, which is not heated, and as alcohol, Guri was replaced with phosphorus, and pentaerythritol was used 13 (+ , Rosinnisdel was obtained in the same manner as in Comparative Example 2.

The conditions of each Example are summarized in Table 2, and the constants of the rosin ester obtained in each Example are shown in Table 3.

The thermal stability and oxygen stability of the rosin esters in Table 3 were measured using the following method.

Thermal Stability Each day, 3 g of the gin ester was placed in a colorimetric tube with an inner diameter of 10 mm and a length of 15 cm, heated to 1, and placed in a thermostat at 180'C for fusion welding. Measured with Cardner Himura 61.

4 g of each L'' gin ester and 6 g of aluminum oxide, which were made into fine powder in an oxygen stability mortar, were mixed uniformly to prepare C sample. This sample was cut into a 7-ray diameter (diameter 60n1m, height 15mm).
), accurately weighed, and kept in a thermostat at 110°C. After 10 days and 20 sips, the mixture was accurately weighed again, and the weight increase rate (%) of the rosin ester due to oxygen absorption was determined by calculation.

As is clear from Table 3, the rosin ester obtained according to the present invention had a low color number, was light in color, and had improved thermal stability and oxygen stability.

Claims (1)

[Claims] 1 Method for producing a rosin ester 2, characterized in that a metal disproportionation catalyst for rosin is mixed together during the esterification reaction of distilled 1] gin with an alcohol. Method 3 for producing rosin Nisdel according to claim 1, characterized in that the metal disproportionation catalyst is parasium\carbon. 1gJ S'F Method for producing 1'' synester according to claim 1