CN102336657A - Purification method for acrylpimaric acid - Google Patents

Abstract

The invention relates to a method for purifying acrylic pimaric acid, comprising the following steps: the first step: mixing acrylic rosin with an organic solvent at a ratio of 1:1 to 10 g/mL, heating to reflux, cooling, standing, filtering, and mixing Washing and drying with an organic solvent to obtain the crude product of acrylpimaric acid; the second step: mixing the crude product of acrylpimaric acid obtained in the first step with an organic solvent in a ratio of 1:2~8g/mL, heating to reflux, filtering while hot, and the filtrate Stand to crystallize, filter under reduced pressure, and dry to obtain high-purity acrylpimaric acid. The method has the advantages of low cost, safe and convenient operation, high yield and high purity of acrylopimaric acid.

Description

A kind of purification method of propylene pimaric acid

technical field

The invention relates to a method for purifying rosin derivatives, in particular to a method for purifying propylene pimaric acid.

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Background technique

Rosin is one of the main forestry products in my country, with an annual output of about 1.1 million tons. The characteristics of the molecular structure of rosin make it have excellent properties such as insulation, adhesion, emulsification and viscosity increasing. Utilizing reactive groups such as carboxyl groups and conjugated double bonds in the molecular structure of rosin, deep-processed products such as polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, acrylic rosin and various rosin esters can be obtained through polymerization and addition reactions. It can be further modified to synthesize high value-added fine chemicals and new polymer materials with different properties and varieties.

Acrylic pimaric acid is the main component of acrylic rosin. It is an organic acid containing two carboxyl groups, which can be used to replace some petrochemical raw materials, such as terephthalic acid, to prepare polyester or polyamide. When propylene pimaric acid is used in the synthesis of polyester, the hydrogenated phenanthrene ring structure in its molecular structure may improve the heat resistance of polyester. But because the composition of acrylic rosin is very complicated, except the main component propylene pimaric acid, there are unreacted resin acids, including abietic acid type resin acid, pimaric acid type resin acid and neutral substances, etc., their physical and chemical properties Similar, and propylene pimaric acid itself is also an isomer, which makes the separation of propylene pimaric acid more difficult. At present, there are roughly two methods for separating propylene pimaric acid:

Propylenepimaric acid structural formula:

(1) Chemical method Propylenepimaric acid is derived from the Diels-Alder addition reaction product of L-pimaric acid and acrylic acid. From the perspective of molecular structure, it contains two carboxyl groups, one of which is connected to the tertiary On the carbon atom, a carboxyl group is connected to the secondary carbon atom, and the reactivity of the two carboxyl groups has a certain difference, and the unreacted resin acids are all monobasic acids. Utilizing the difference in reactivity between the two carboxyl groups, propylene pimaric acid can be separated step by step after alkalization. For example: after Xie Hui et al. alkalized acrylic acid rosin, extracted with ether to remove the neutral substance, adjusted the pH value of the solution to 6.5, filtered to remove the unreacted resin acid precipitate, and continued to add acid until no precipitate was formed to obtain propylene pimaric acid. The crude product was further recrystallized in benzene to obtain propylene pimaric acid. Mao Yingli and others crushed acrylic rosin, added dilute alkali solution to dissolve it, added acid to adjust the pH to 6.5, removed the precipitate, then added excess acid to the filtrate to pH 1, washed and dried the precipitate several times, and then used Wash with petroleum ether several times until the filtrate is colorless, and finally vacuum-dry the precipitate to constant weight to obtain acrylpimaric acid.

(2) Physical method Due to the difference in molecular structure between acrylic pimaric acid and unreacted resin acid, their solubility in solvents is quite different. Sabyasachi Sinha Roy et al. used ether to dissolve acrylic acid rosin, and then precipitated it with petroleum ether. After repeated repetitions, acrylic pimaric acid could be obtained. Because other resin acids and neutrals have a certain solubility in petroleum ether, this method needs to be repeated many times and the purity is not high, the yield is low, the energy and power costs are high, and the purification cost increases. The above-mentioned methods all have the disadvantages of complex purification steps, high toxicity of solvents and low purification efficiency to varying degrees.

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Contents of the invention

In order to solve the disadvantages of high cost, low yield and low purity of preparing propylene pimaric acid in the prior art, the invention provides a method for purifying propylene pimaric acid.

The technical scheme of the present invention is: a kind of purification method of acrylic pimaric acid, adopts physical method to carry out purification, the first step, acrylic acid rosin is mixed with organic solvent, heating, reflux, cooling, stand still, filter, adopt organic solvent to wash, drying to obtain the crude product of propylene pimaric acid; in the second step, the crude product of propylene pimaric acid is recrystallized with an organic solvent, and the organic solvent is any one of petroleum ether or ethyl acetate or a mixture of the two in any ratio, The purity of the obtained propylene pimaric acid is more than or equal to 98%wt.

In the first step, the acrylic rosin and the organic solvent are added according to the mass volume ratio of 1:1~10g/ml.

During the second step of recrystallization, the mass volume ratio of the crude product of propylene pimaric acid to the organic solvent is 1:2~8g/ml.

The acrylic rosin is prepared by Diels-Alder addition reaction of rosin or rosin resin acid and acrylic acid.

The rosin or rosin resin acid is derived from gum rosin, wood rosin or tall oil rosin.

The used organic solvent is recycled for reuse.

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Beneficial effect:

(1) The physical method of washing, separation and recrystallization is adopted, which is simple and convenient to operate;

(2) The organic solvents used are petroleum ether and ethyl acetate, with low toxicity;

(3) The organic solvents used are petroleum ether and ethyl acetate, which can be recycled and reused, and the cost is low;

(4) The purity of the obtained propylene pimaric acid is above 98%.

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Description of drawings

Figure 1 is the GC chart of raw resin acid.

Figure 2 is the GC chart of acrylic rosin.

Fig. 3 is the GC chart of propylene pimaric acid crude product.

Fig. 4 is the GC figure of the propylene pimaric acid of recrystallization purification.

Fig. 5 is the mass spectrogram of the propylene pimaric acid of recrystallization purification.

Fig. 6 is the ¹ H NMR spectrum of recrystallized and purified propylene pimaric acid.

Fig. 7 is the ¹³ C NMR spectrum of recrystallized and purified propylene pimaric acid.

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Detailed ways

In order to better implement the present invention, it is given as an example, but not to limit the present invention.

A method for purifying propylene pimaric acid, comprising the following steps:

In the first step, crush the acrylic rosin and place it in a four-necked reaction flask, add a mixed organic solvent in a ratio of 1:1~10g/mL, start stirring and heat to reflux, cool after 3 hours, stand still, filter, and use The mixed organic solvent is washed and dried to obtain the crude product of propylene pimaric acid; the organic solvent is a mixture of petroleum ether and ethyl acetate in any proportion.

In the second step, place the crude product of propylene pimaric acid obtained in the first step in a four-necked reaction flask, add an organic solvent in a ratio of 1:2~8g/mL, start stirring and heat to reflux, filter while hot, and let the filtrate stand Crystallization, suction filtration under reduced pressure, drying to obtain propylene pimaric acid, the organic solvent is a mixture of petroleum ether and ethyl acetate in any proportion, preferably petroleum ether and ethyl acetate according to the volume ratio of 70 ~ 95:30 ~ 5 Proportional mix.

The synthesis of acrylic rosin is a conventional method. Specifically, the acrylic rosin is prepared by reacting abietic acid and acrylic acid at a mass ratio of 100:20-30 at a temperature of 150-230° C. for 3-7 hours. If there are any references for the preparation of acrylic rosin, I attach it here. If the preparation of acrylic rosin is a conventional method, and as long as it is acrylic rosin, you can use your method for purification. The focus should not be on the preparation of acrylic rosin. Regarding your purification, it is enough to write the corresponding steps of purification in detail in the examples.

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Example 1

Add 200.0 g of rosin resin acid to a 500 mL four-neck flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, start stirring under nitrogen protection and raise the temperature to 160 ° C, dropwise add 51.0 g of acrylic acid to the reaction flask within 1 h , after the dropwise addition, the temperature was gradually raised to 230°C within 2 hours, the reaction was continued for 3 hours, the temperature was lowered to 170°C and the material was discharged to obtain acrylic rosin.

Take 100.0g of the above-mentioned acrylic rosin, pulverize it and add it to a 1000mL four-necked flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, and add 500mL of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 85:15 In a four-neck flask, heat until the solvent refluxes to start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 52.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-necked flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 100mL ethyl acetate and join in the four-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while it is hot, let the filtrate stand still, and after acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, and dry in vacuo to obtain 17.0 g propylene pimaric acid, the yield of propylene pimaric acid is 63%, and the purity is 98.5%.

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Example 2

Get 100.0g of acrylic rosin in Example 1, put it into a 1000mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen conduit and a reflux condenser after pulverization, measure the petroleum ether/ethyl acetate mixed with a volume ratio of 90:10 Add 500 mL of solvent into a four-neck flask, heat until the solvent refluxes and start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 65.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-neck flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 80mL ethyl acetate and join in the four-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while it is hot, let the filtrate stand still, after acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, and vacuum dry to obtain 18.0 g propylene pimaric acid, the yield of propylene pimaric acid is 83%, and the purity is 98.1%.

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Example 3

Get 50.0g of acrylic rosin in Example 1, put it into a 500mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen conduit and a reflux condenser after pulverization, and measure the petroleum ether/ethyl acetate mixed with a volume ratio of 80:20 Add 200 mL of solvent into a four-neck flask, heat until the solvent refluxes and start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 22.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-neck flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 80mL ethyl acetate and join in the four-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while it is hot, let the filtrate stand still, and after acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 90:10, and vacuum-dry to obtain 16.0 g propylene pimaric acid, the yield of propylene pimaric acid is 50%, and the purity is 98.7%.

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Example 4

Add 200.0 g of rosin resin acid to a 500 mL four-neck flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, start stirring under nitrogen protection and raise the temperature to 160 ° C, and drop 54.0 g of acrylic acid into the reaction flask within 1 hour , after the dropwise addition, the temperature was gradually raised to 210°C within 2 hours, the reaction was continued for 3 hours, the temperature was lowered to 170°C and the material was discharged to obtain acrylic rosin.

Take 100.0g of the above-mentioned acrylic rosin, pulverize it and add it to a 1000mL four-necked flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, and add 400mL of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 80:20 In a four-neck flask, heat until the solvent refluxes to start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 54.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-neck flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 80mL ethyl acetate and join in the four-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while it is hot, let the filtrate stand still, after acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, and vacuum dry to obtain 18.0 g propylene pimaric acid, the yield of propylene pimaric acid is 69%, and the purity is 98.8%.

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Example 5

Add 200.0 g of rosin to a 500 mL four-neck flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, start stirring under nitrogen protection and raise the temperature to 160 ° C, drop 46.0 g of acrylic acid into the reaction flask within 1 h, drop After the addition, the temperature was gradually raised to 220°C within 2 hours, the reaction was continued for 3 hours, the temperature was lowered to 170°C and the material was discharged to obtain acrylic rosin.

Take 100.0g of the above-mentioned acrylic rosin, pulverize it and add it to a 1000mL four-necked flask equipped with a stirrer, thermometer, nitrogen conduit and reflux condenser, and add 500mL of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 85:15 In a four-neck flask, heat until the solvent refluxes to start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 48.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-necked flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 75mL ethyl acetate and join in the 4-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while hot, and let the filtrate stand still. After acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, and vacuum-dry to obtain 17.5 g propylene pimaric acid, the yield of propylene pimaric acid is 60%, and the purity is 97.8%.

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Example 6

Get 50.0g of acrylic rosin in Example 5, put it into a 500mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen conduit and a reflux condenser after pulverization, measure petroleum ether/ethyl acetate with a volume ratio of 95:5 and mix Add 250 mL of solvent into a four-neck flask, heat until the solvent refluxes and start timing, and stop heating after 3 hours. After cooling to room temperature, continue to stir for 3 hours, vacuum filter, wash 3 times with a mixed solvent of petroleum ether/ethyl acetate with a volume ratio of 95:5, and dry in vacuum to obtain 30.0 g of crude propylene pimaric acid.

Add 20.0g of propylene pimaric acid crude product into the 250mL four-neck flask equipped with stirrer, thermometer, nitrogen conduit and reflux condenser, measure 80mL ethyl acetate and join in the four-necked flask, heat to solvent reflux, propylene pimaric acid After completely dissolving, filter while it is hot, let the filtrate stand still, and after acrylopimaric acid is fully crystallized, filter under reduced pressure, wash 3 times with a small amount of petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, and dry in vacuo to obtain 16.8 g propylene pimaric acid, the yield of propylene pimaric acid is 72%, and the purity is 97.5%.

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Example 7

Get 50.0g of acrylic rosin in Example 5, pulverize it and add it to a 500mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen conduit and a reflux condenser, measure 250mL of ethyl acetate and add it to the four-necked flask, and heat to Solvent reflux starts timing, and stops heating after 3h. After cooling to room temperature, stirring was continued for 3 hours, but no solid matter remained. Then it is not feasible to completely adopt ethyl acetate to carry out the purification of the crude product of acrylopimaric acid.

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Example 8

Get 50.0g of acrylic rosin in Example 5, pulverize it and add it to a 500mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen conduit and a reflux condenser, measure 250mL of petroleum ether and add it to the four-necked flask, and heat until the solvent Reflux starts timing, and stops heating after 3h. Continue to stir for 3 hours after being cooled to room temperature, vacuum suction filtration, wash 3 times with sherwood oil, vacuum-dry, namely obtain 47g propylene pimaric acid crude product, through gas chromatographic analysis, also contain a large amount of unreacted resin acid in the propylene pimaric acid crude product . Then it is not feasible to completely adopt petroleum ether to carry out the purification of the crude product of acrylopimaric acid.

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Product analysis

The chromatographic analysis of resin acid, acrylic rosin, propylene pimaric acid etc. in embodiment 1 all adopts tetramethyl ammonium hydroxide to carry out methylation reaction earlier, generates corresponding resinous acid methyl ester, acrylate rosin methyl ester and propylene pimaric acid acid dimethyl ester, etc., which is beneficial to their gasification for chromatographic separation and qualitative and quantitative analysis.

Figure 1 is the GC chart of the raw material resin acid. The chromatographic peaks at the retention time between 5.5min and 9min are identified as pimaric acid, isopimaric acid, palusmaric acid, dehydroabietic acid, abietic acid and neoabietic acid. ;

Figure 2 is the GC chart of acrylic rosin. The chromatographic peaks at the retention time between 5.5min and 9min are obviously weakened, that is, they are involved in the Diels-Alder reaction with acrylic acid, and the retention time is between 11min and 15min. The chromatographic peak is identified as the isomer of propylene pimaric acid;

Figure 3 is the GC chart of the crude product of propylene pimaric acid, the acrylic acid rosin generated by the Diels-Alder addition reaction of acrylic acid and abietic acid, after washing and drying with petroleum ether/ethyl acetate at a volume ratio of 85:15, the retention time is 5.5 The chromatographic peaks between min and 9 min basically disappear;

Fig. 4 is the GC figure of the propylene pimaric acid of recrystallization purification, the chromatographic peak of propylene pimaric acid crude product after ethyl acetate recrystallization, main chromatographic peak is 12.45min, and its content is analyzed as 93% through area normalization method, The substance corresponding to the chromatographic peaks whose retention time is 12.68min and 13.55min is also acrylopimaric acid of a certain stereo configuration;

Fig. 5 is the mass spectrogram of the propylene pimaric acid that recrystallization purifies, and its molecular weight of the propylene pimaric acid dimethyl ester that generates after propylene pimaric acid methylation is 402, is identical with the molecular ion peak in the spectrogram;

Fig. 6 is the ¹ H NMR spectrogram of the propylene pimaric acid of recrystallization purification;

Figure 7 is the ¹³ C NMR spectrum of propylene pimaric acid purified by recrystallization. By analyzing its carbon and hydrogen nuclear magnetic resonance spectra, the molecular structure of the purified propylene pimaric acid is in line with expectations.

Claims (6)

1. the method for purification of a rosin acrylic acid adopts physical method to purify, and the first step is mixed acrylic acid rosin with organic solvent, and heating, backflow are cooled off, leave standstill, filtered, and adopts organic solvent washing, drying to obtain the rosin acrylic acid bullion; Second step, adopt organic solvent to carry out recrystallization the rosin acrylic acid bullion and promptly get, it is characterized in that, described organic solvent be in sherwood oil or the ETHYLE ACETATE any one or both arbitrarily than mixture, the purity >=98%wt of the rosin acrylic acid that obtains.

2. the method for purification of rosin acrylic acid as claimed in claim 1 is characterized in that, acrylic acid rosin and organic solvent are the ratio interpolation of 1:1 ~ 10g/mL according to mass volume ratio in the first step.

3. the method for purification of rosin acrylic acid as claimed in claim 1 is characterized in that, second step, the mass volume ratio of rosin acrylic acid bullion and organic solvent was 1:2 ~ 8g/mL during recrystallization.

4. the method for purification of rosin acrylic acid as claimed in claim 1 is characterized in that, described acrylic acid rosin is that rosin or rosin acid and vinylformic acid carry out Di Ersi-A Erde addition reaction and makes.

5. the method for purification of rosin acrylic acid as claimed in claim 4 is characterized in that, described rosin or rosin acid derive from gum resin, wood rosin or starex.

6. the method for purification of rosin acrylic acid as claimed in claim 1 is characterized in that, used organic solvent reclaims and reuses.

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