CN1116370C - Esterification process of rosin acid and its derivative - Google Patents

Abstract

The present invention relates to the esterification method of rosin resin acid and its derivatives. Rosin esterification can overcome the shortcomings of rosin resources and broaden its application field, but the current esterification reaction is not ideal due to the catalyst. The invention provides a supported type clay catalyst. The esterification reaction introduced by the catalyst has the advantages of short reaction time, low temperature, uniform and transparent esterification product, light color and no post-treatment, which provides a new way for modern industrial production. .

Description

A kind of esterification method of rosin resin acid and its derivatives

The invention relates to a method for esterification of a class of rosin resin and derivatives thereof.

Rosin is the largest forest product resource in China. As a natural resin with excellent performance, rosin has been widely used. However, rosin is brittle, easy to oxidize and discolor, and has a high acid value, which hinders its application to a certain extent. Esterification Modification is one of the most basic and important means to broaden the application of rosin. The performance of rosin is greatly improved after modification. Various rosin esters account for more than 60% of rosin modified products. Its polyols are widely used in coatings and inks. , rubber, adhesives and other industries as tackifiers, monohydric alcohol esters can be used as processing aids for rubber and plastics, the catalysts of rosin and its derivatives commonly used now include zinc oxide, etc., the process of using these catalysts requires high temperature (250 ~ 300 ℃) The reaction time is longer (7～11h) (Modern Chemical Industry, 1994, 2, p43).

The purpose of the present invention is to provide a high-efficiency, low-energy-consumption catalyst for the rosin esterification modification industry, and to synthesize rosin resin acid and its derivatives through efficient, low-energy catalytic esterification. kind.

For the esterification reaction of rosin resin acid and its derivatives in the present invention, the new catalyst cited is mainly supported Ln ₂ O ₃ /Al ₂ O ₃ alkene catalyst, wherein Ln represents an alkene element with an atomic number between 57 and 71 , especially Nd, Sm, Gd, La, Eu, Er, etc., as highly active catalysts for the esterification of rosin resin, compared with traditional catalytic processes, the use of supported alkene catalysts can catalyze the esterification of rosin resin acids and their derivatives When the esterification reaction time is shortened, the reaction temperature is significantly lowered, the esterification product is uniform and transparent, and the color is light, so that the esterification modification process of rosin resin acid and its derivatives can be better suitable for the development of modern production.

Esterification method provided by the present invention comprises following process:

First prepare the catalyst: take a kind of Ln ₂ O ₃ (Ln=Nd, Sm, Gd, La, Eu, Er), add an appropriate amount of nitric acid to make alkene nitrate, and take a measured amount of AlCl ₃ to make an aqueous solution. Mix the two solutions, and titrate with concentrated ammonia water to make it precipitate, control its pH=8~10, make the Al(OH) ₃ and Ln(OH) ₃ co-precipitate uniformly and completely, filter with suction, dry, and dry at 800°C Dry for 1 hour to obtain a supported Ln ₂ O ₃ /Al ₂ O ₃ catalyst. Add this catalyst to the reaction system of rosin resin acid or its derivatives and alcohol, stir, heat, and raise the temperature to a certain temperature (200-260°C ), temperature control, and reacted for 2 to 6 hours. After the esterification reaction water yield reached the theoretical value, the residual solvent and alcohols could be evaporated to obtain the ester of rosin or its derivatives. The conversion rate can reach more than 90%. The consumption of catalyst It is 0.05% to 1.5% of the weight of rosin resin acid or its derivatives. The number of carbon atoms in the reaction system is 1 to 18, and solvent dehydration can be used. The alcohols in the reaction system are aliphatic alcohols and aromatic alcohols, preferably carbon atoms 1-18 Alcohols, especially monohydric, dihydric, trihydric or tetrahydric alcohols.

Example 1 Supported Ln ₂ O ₃ /Al ₂ O ₃ catalyst preparation method:

Take 1.0 g of a kind of Nd2O3, add an appropriate amount of nitric acid (about 5ml) to dissolve it, and make it into an aqueous solution of alkene nitrate, and take another 10.0 g of _AlCl3 to make an aqueous solution, mix the above two solutions, and titrate with concentrated ammonia water to make it Co-precipitation occurs, and its pH is controlled to 10, so that the co-precipitation of AL(OH) ₃ and Nd(OH) ₃ is uniform and complete, Na ₂ O ₃ /Al ₂ O ₃ is filtered by suction, and dried at 800°C for 1 hour to obtain the supported type Nd ₂ O ₃ /Al ₂ O ₃ catalyst.

Example 2:

Get 0.5 mol of rosin resin acid, 0.6 mol of isooctyl alcohol, 2 grams of Nd ₂ O ₃ /Al ₂ O ₃ , put into a four-neck round bottom equipped with dropping funnel, thermometer, stirrer, reflux condenser and water separator In the flask, heat and stir with an electric heating mantle. When the temperature rises to 220°C, add an appropriate amount of toluene to the reaction system to dehydrate. Theoretical amount; distill off residual toluene and isooctyl alcohol; stop heating, let stand and cool to 100°C, pour out the reaction product, the conversion rate is greater than 96%.

Example 3:

Get 0.5 mole of rosin resin acid, 1..5 gram of Sm ₂ O ₃ /Al ₂ O ₃ , put into a four-neck round bottom flask equipped with dropping funnel, thermometer, stirrer, reflux condenser and water separator, Heat and stir with an electric heating mantle. When the temperature rises to 240°C, add the calculated amount of lauryl alcohol dropwise to the reaction system, control the dropping speed to keep the temperature at about 230°C, and time it. After 3.5 hours, the water comes out of the water separator The theoretical amount has been reached; the residual lauryl alcohol is distilled off; the heating is stopped, and the reaction product is poured out, and the conversion rate is greater than 94%.

Example 4:

Get 0.5 mole of disproportionated rosin resin acid, 0.3 mole of diethylene glycol, 0.5 gram of Gd ₂ O ₃ /Al ₂ O ₃ , put into a four-neck circle equipped with dropping funnel, thermometer, stirrer, reflux condenser and water separator In the bottom flask, heat and stir with an electric heating mantle. When the temperature rises to 240°C, add an appropriate amount of toluene to the reaction system for dehydration. to the theoretical amount; distill off residual toluene and diethylene glycol; stop heating, let stand and cool to 100°C, pour out the reaction product, and the conversion rate is greater than 91%.

Embodiment 5: Get 0.4 mole of hydrogenated rosin resin acid, 0.1 mole of pentaerythritol, 0.3 gram of Eu ₂ O ₃ /Al ₂ O ₃ , put into a four-necked round bottom flask equipped with dropping funnel, reflux condenser, thermometer and stirrer During the process, heat with an electric heating mantle, stir, control the reaction temperature at about 260°C and record the time. After 2.5 hours, the water in the water separator has reached the theoretical amount; evaporate the residual alcohol; stop heating, and let it cool down to 150°C. The reaction product was poured out, and the conversion rate was greater than 96%.

Embodiment 6:

Get 0.6 mol of rosin resin acid, 0.2 mol of glycerin, 0.2 gram of Er ₂ O ₃ /Al ₂ O ₃ , put in a four-necked round bottom flask equipped with a dropping funnel, reflux condenser, thermometer and stirrer, and use an electric heating mantle Heating and stirring, control the reaction temperature at about 240°C, and count the time. After 90 minutes, the water in the water separator has reached the theoretical amount; steam the residual water and glycerin; stop heating, let it stand and cool to 150°C, and pour out the reaction product , The conversion rate is greater than 98%.

Embodiment 7:

Get 0.5 moles of hydrogenated rosin resin acid, 0.6 moles of benzyl alcohol, and 0.1 gram of La ₂ O ₃ , put them into a four-necked round-bottomed flask equipped with a dropping funnel, a thermometer, a stirrer, a reflux condenser and a water separator, and use an electric heating Heating and stirring, when the temperature rises to 200°C, add an appropriate amount of toluene dropwise to the reaction system for dehydration, control the reaction temperature at about 200°C, and record the time. After 90 minutes, the water in the water separator has reached the theoretical amount; Residual toluene and benzyl alcohol; stop heating, let stand and cool to 100°C, pour out the reaction product, the conversion rate is greater than 97%.

Claims (6)

1, a kind of esterification process of rosin acid or derivatives thereof is characterized in that adding in the reaction system carried Ln ₂O ₃/ Al ₂O ₃Alkene soil catalyst, this method comprises following process:

1). Kaolinite Preparation of Catalyst at first: get a kind of Ln ₂O ₃, add nitric acid and make alkene soil nitrate, with itself and AlCl ₃Aqueous solution, with the concentrated ammonia liquor titration it, make it to produce co-precipitation, control PH=8～10, precipitation fully after, suction filtration, oven dry makes Ln ₂O ₃/ Al ₂O ₃The type CatalystT.

2). with above-mentioned 1) in the catalyzer that makes join in the reaction system of rosin acid or derivatives thereof and alcohol, catalyst levels is 0.05～1.5% of a rosin acid or derivatives thereof weight, 200～260 ℃ of controlled temperature, reacted 2～6 hours, and obtained the ester class of rosin acid or derivatives thereof.

2, according to the esterification process described in the claim 1, it is characterized in that described carried Ln ₂O ₃/ Al ₂O ₃Alkene soil catalyst, wherein Ln represents the rare-earth element of atomic number between 57～71.

3, according to the esterification process described in claim 1 or 2, that it is characterized in that described Ln representative is Nd, Sm, Gd, La, Eu or Er.

4,, it is characterized in that the alcohols in the reaction system comprises Fatty Alcohol(C12-C14 and C12-C18) and aromatic alcohol according to the esterification process described in the claim 1.

5,, it is characterized in that the alcohol in the reaction system is monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, or quaternary alcohols according to the esterification process described in claim 1 or 4.

6,, it is characterized in that alcohol in the reaction system is 1～18 alcohols according to the esterification process described in claim 1 or 4.