CN104693024B - Rosin triol ester as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a rosin triol ester and a preparation method thereof. The chemical name of the rosin triol ester is dehydroabietic acid trimethylol propane ester. The preparation method of rosin triol ester is: take dehydroabietic acid and trimethylol propane as raw material, take EDC/DMAP as catalyst, any one in methylene chloride, tetrahydrofuran and N,N-dimethylformamide As a solvent, an esterification reaction occurs at room temperature to synthesize dehydroabietic acid trimethylol propane ester. The esterification method is completed in one step, can effectively overcome steric hindrance, has high yield, reacts at room temperature, reduces energy consumption, by-products are soluble in water and can be easily purified, has low odor and less waste, and has a wide range of solvents to choose from. The ester prepared by the present invention has a wide range of uses, such as plasticizers and modifiers that can be used for various resins, adhesives that can form good pressure-sensitive and heat-sensitive adhesive tapes, used for hot-melt coatings, surface Active agent and pharmaceutically acceptable carrier.

Description

A kind of rosin triol ester and its preparation method and application

technical field

The invention relates to the technical field of rosin essence deep processing, in particular to a rosin triol ester, a preparation method and application thereof.

Background technique

Rosin is a kind of natural resin, and its raw material comes from renewable pine forest resources. It is one of the most important products in my country's forest chemical industry. my country's annual output of rosin is more than 800,000 tons, and it is one of the main exporting countries of rosin, accounting for 60% of the world's trade volume. Most developed countries rely on imports of rosin. The main component of rosin is resin acid, accounting for 85% to 90% of the total mass. They are a class of monocarboxylic acids with two double bonds each having a tricyclic phenanthrene skeleton. The unique chemical structure of rosin makes it have excellent environment-friendly properties, such as anti-corrosion, moisture-proof, insulation, adhesion, emulsification, softening, etc. Rosin and its derivatives are widely used in pigments, varnishes, inks, and paper molding; they are also used in chewing gum, pesticide industry, electronics industry, dental field and cosmetics industry. At present, the synthesis of rosin-based polymers has become a research hotspot at home and abroad. Researchers have successfully prepared a variety of rosin-based functional polymers and applied them in various fields such as medicine, coating materials, food additives, chemical catalysis, environmental protection, and adsorption and separation. However, the carboxyl group of rosin is located on the tertiary carbon atom, the steric hindrance is large, and the reaction conditions are harsh, which are common problems in the esterification process of rosin. At present, there are mainly three kinds of rosin esterification methods: proton acid catalysis, solid acid catalysis and acid chloride esterification.

Protic acid is a common catalyst for the esterification of alkyds, and it is also effective for the esterification of rosin. In the reaction, the protonic acid first protonates the carbonyl of the resin acid, making it easier to undergo nucleophilic addition with the alcohol, then transfers the proton, eliminates the water molecule, and then eliminates the proton to form an ester (SN2 mechanism). Commonly used protonic acids mainly include sulfuric acid, phosphoric acid, hypophosphorous acid, boric acid, benzenesulfonic acid and p-benzenesulfonic acid. This method has the advantages of wide source of catalyst, cheap and easy to obtain, good catalytic effect, etc., but has disadvantages such as corrosion of equipment, difficulty in separating catalyst and product, etc., and has been replaced by other methods in production.

Solid acid catalysis is a substance that promotes chemical reactions by means of acidic substances on the surface of solids, and its catalytic mechanism is similar to that of protonic acids. Commonly used solid acids are mainly Zn ²⁺ solid acids, such as ZnO, ZnCl ₂ :, ZnS0 ₄ , Zn(OAC) ₂ and so on. The solid acid catalysis method has the advantages of non-corrosion equipment, easy separation, and reusability, but it needs heating, the product is easily oxidized, and the color becomes darker.

The acid chloride esterification method is to first convert the resin acid of rosin into acid chloride, and then alcoholyze the acid chloride to obtain the corresponding ester. Commonly used acid chloride reagents include newly prepared thionyl chloride (SOCl ₂ ), oxalyl chloride (C ₂ O ₂ Cl ₂ ) , Phosgene (COCl ₂ ), etc. The acid chloride esterification method has mild conditions and high yield; but its disadvantage is that the reaction conditions need to be strictly controlled when preparing the acid chloride, it is not easy to remove excess SOCl _{2 ,} the equipment is severely corroded, and the acid chloride needs to be produced and used immediately. , keep anhydrous and dry, harsh conditions, step-by-step reaction, time-consuming.

In view of the problems existing in the above-mentioned several rosin esterification methods, the present invention introduces the Steglich esterification method into the rosin esterification process.

The main component of rosin is resin acid. Common resin acids can be divided into abietic type resin acid, pimaric acid, isopimaric acid type resin acid and Laudan type resin acid according to the position of the alkyl group and double bond. Among them, abietic acid is the main component of natural resin rosin, and its content is 45%-54%. an isopropyl group. Because abietic acid contains high-energy conjugated double bonds, the properties of rosin are extremely unstable, and it is easily oxidized by oxygen in the air to produce dark-colored oxidized rosin. In order to change the unstable structure of the conjugated double bond, abietic acid has a tendency to be dehydrogenated into a benzene ring by disproportionation reaction or converted into a relatively stable form by removing the double bond by hydrogenation.

The present invention will use dehydroabietic acid and trimethylolpropane as raw materials to generate a new rosin triol ester through the Steglich esterification method, which has not been reported so far.

Contents of the invention

The object of the present invention is to provide a kind of rosin triol ester and its preparation method and application, the present invention is that dehydroabietic acid trimethylol propane is prepared by Steglich esterification method by taking dehydroabietic acid and trimethylol propane as raw material ester. The Steglich esterification method means that EDC-DMAP is used as a catalyst at room temperature to effectively overcome the steric hindrance of the reactants to synthesize esters. Steglich esterification method, which is completed in one step, effectively overcomes steric hindrance, high yield, reacts at room temperature, reduces energy consumption, by-products are soluble in water and easy to purify, has low odor and less waste, and has a wide range of solvent choices, avoiding the above-mentioned esterification The problem of the existence of the chemical method. The trimethylolpropane dehydroabietate prepared by the invention has wide application.

For realizing above object, the technical scheme that the present invention adopts is:

The first object of the present invention is to provide a new compound: rosin triol ester.

A kind of rosin triol ester, the chemical name of this compound is: dehydroabietic acid trimethylol propane ester, and its chemical structural formula is:

The appearance of the compound is white strip crystal; odorless; solubility: slightly soluble in water, completely soluble in ethanol, petroleum ether, dichloromethane and ethyl acetate organic solvents; decomposition temperature: 250-430°C; its molecular formula is C ₂₆ H ₄₀ O _{4 ;} molecular weight: 416.61.

The English name of the compound is: trimethylolpropane dehydroabietyate.

For the above compounds, the applicant has not found substances with the same structure and the same physical and chemical properties.

Second object of the present invention is to provide a kind of preparation method of rosin triol ester.

A preparation method of rosin triol ester: take dehydroabietic acid and trimethylolpropane as raw materials, use EDC/DMAP as a catalyst, and synthesize dehydroabietic acid triol by esterification reaction in an organic solvent and at normal temperature Methyl propane ester, the reaction formula is:

The mass ratio of the above-mentioned reaction materials is: dehydroabietic acid:trimethylolpropane:DMAP:EDC=1.5:0.67～4.02:0.12～1:1.15～1.725.

The EDC is a water-soluble carbodiimide, which is used as an activating reagent for carboxyl groups in the esterification reaction. In organic chemistry, carboxylic acid and alcohol are esterified with EDC and catalyst 4-dimethylaminopyridine (DMAP). . EDC only plays the role of activating the carboxyl group in the reaction process, and what plays a catalytic role is DMAP, and the amount of EDC substance is greater than the amount of dehydroabietic acid substance, so that the carboxyl group can be fully activated.

The organic solvent mentioned above is any one of dichloromethane, tetrahydrofuran and N,N-dimethylformamide.

The chemical name of DMAP is 4-dimethylaminopyridine, and the chemical name of EDC is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

The specific steps of the preparation method of a kind of rosin triol ester described above include:

1) Add materials for reaction: Add dehydroabietic acid and trimethylolpropane raw materials into a reaction vessel that has excluded oxygen, and add DMAP (4-dimethylaminopyridine), dissolve them in dichloromethane or tetrahydrofuran Or any organic solvent of N, N-dimethylformamide, its consumption is: dehydroabietic acid: organic solvent=1g: 12～20mL, after dissolving, cool down and make the temperature cool to 0 ℃, add EDC (1 -(3-Dimethylaminopropyl)-3-ethylcarbodiimide), cut off oxygen, react for 15-30 minutes, return to normal temperature to continue the reaction, stop stirring after 10-24 hours, and the reaction is over. After the above reaction The material is rotated and evaporated to remove the solvent to obtain a solid mixture;

2) Preparation of the crude product: dissolve the above solid mixture with a solvent, wash with saturated brine, take the organic layer, and spin dry to obtain the crude product of trimethylolpropane dehydroabietic acid;

3) Purification of the product: the crude product of trimethylolpropane dehydroabietate was separated by column chromatography to obtain a compound in the form of white strip crystals, which was confirmed to be trimethylolpropane dehydroabietate by structural testing ester.

Furthermore, the normal temperature of step 1) is 15-30°C, preferably 20-28°C.

Furthermore, the stirring reaction time is preferably 14-18 hours.

The solvent of the step 2) is selected from any one of petroleum ether, ethanol, methylene chloride and ethyl acetate.

The oxygen exclusion and oxygen isolation can be achieved by feeding inert gases such as nitrogen, argon, and helium.

The solvent used in the rotary evaporation is petroleum ether, and the consumption is 50-200 mL.

The temperature of the rotary steaming is 40-50° C., the pressure is 0.007-0.009 MPa, and the rotary steaming time is 20-45 minutes.

Described column chromatography is silica gel column chromatography.

The adsorbent used in the column chromatography is silica gel.

The column chromatography eluent is a petroleum ether/ethyl acetate system, and the amount used is 2/1 to 3/1 of the column volume.

Furthermore, the purity of the trimethylolpropane dehydroabietate prepared by the method is as high as 95.5% or more as measured by high performance liquid chromatography.

The 3rd object among the present invention is to provide the purposes of rosin triol ester:

Rosin triol ester is a kind of new abietyl alcohol among the present invention, and trimethylol propane dehydroabietate has two -OH functional groups, has wide application, can be used for polycondensation synthetic polyester etc., for example with Diacid condensation polymerizes into amphiphilic polycondensate, which can form a good adhesive for pressure-sensitive and heat-sensitive adhesive tapes; and because rosin triol ester contains dehydroabietic acid group and has a fused multi-finger ring rigid structure, it has good Excellent heat resistance, can be used as a plasticizer and modifier for various resins, such as used as a plasticizer in varnishes made of ethyl cellulose, chlorinated rubber, vinyl resin and nitrocellulose, it Together with various film-forming substances, its properties can be improved, such as mixing with water-soluble film-forming substances, casein and zein to improve its adhesion and color stability; when combined with non-water-soluble film-forming substances, it can It can form a good adhesive for pressure-sensitive and heat-sensitive adhesive tapes; when combined with ethyl cellulose and vinyl polymers, it can form hot-melt coatings, etc. It can also form a series of ether derivatives, such as reacting with epoxide to form hydroxyl polyether, which can be used as a surfactant or a pharmaceutical carrier.

The beneficial effect that the present invention obtains:

1. The invention provides a kind of novel compound rosin triol ester, and the chemical name of this compound is dehydroabietic acid trimethylol propane ester. The invention uses the renewable resource rosin as the main raw material to prepare trimethylolpropane dehydroabietate. The cost of the raw material is low and the source is wide. It can replace non-renewable petrochemical products. The preparation process is safe and non-toxic, expanding the scope of our country. Rosin industry, and the prepared rosin triol ester is biodegradable and environmentally friendly.

2. Compared with the dehydroabietic acid monoglyceride, the prepared trimethylolpropane dehydroabietate has three hydroxyl groups which are sterically equivalent, regular in structure, and no isomers.

3. The present invention introduces the Steglich esterification method. This esterification method is completed in one step, effectively overcomes steric hindrance, has high yield, reacts at room temperature, reduces energy consumption, by-products are soluble in water and easy to purify, and the smell is small and waste is less. The range of solvent selection is wide, and the problems existing in the protonic acid catalysis method, solid esterification method and acid chloride esterification method are overcome. The method can be used for efficient preparation of rosin triol ester. The purity of propyl propane ester is as high as 95.5%.

4. Using EDC/DMAP as a catalyst can effectively overcome steric hindrance. Compared with the acid chloride method, the reaction can be completed in one step, with high yield, lower toxicity, wide selection of solvents, milder conditions, and easy purification.

5. Compared with common vacuum distillation, rotary evaporation increases the distillation area. Therefore, the distillation time can be shortened, and there is no need to add zeolite, and the distillation can be performed better.

6. The prepared trimethylolpropane dehydroabietic acid has two -OH functional groups and has a wide range of uses, and can be used for polycondensation to synthesize polyesters, such as polycondensation with diacids to form amphiphilic polycondensates, Makes good adhesive for pressure and heat sensitive adhesive tapes.

7. Due to the introduction of dehydroabietic acid groups into rosin triol esters, it has a rigid structure of fused multi-fingered rings and has good heat resistance. It can be used as a plasticizer and modifier for various resins, such as for ethyl As a plasticizer in varnishes made of cellulose, chlorinated rubber, vinyl resin and nitrocellulose, it can be used together with various film-forming substances to improve its properties, such as water-soluble film-forming substances, Mixing casein and zein improves its adhesion and color stability; when combined with non-water-soluble film-forming substances, it can form a good adhesive for pressure-sensitive and heat-sensitive adhesive tapes; and with ethyl cellulose, vinyl When the polymers are combined, they can form hot-melt coatings and the like. It can also form a series of ether derivatives, such as reacting with epoxides to form hydroxyl polyether, which can be used as a surfactant substance or as a drug carrier.

Description of drawings

Fig. 1 is the infrared spectrogram of dehydroabietyl trimethylolpropane ester

Figure 2 is the H NMR spectrum of dehydroabietyl trimethylolpropane ester

Fig. 3 is the carbon nuclear magnetic resonance spectrogram of dehydroabietyl trimethylol propane ester.

Fig. 4 is the thermogravimetric analysis figure of dehydroabietyl trimethylol propane ester

Fig. 5 is the infrared characterization spectrum of dehydroabietyl succinic acid polyester.

Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of dehydroabietyl succinic acid polyester.

Fig. 7 is the thermogravimetric analysis figure of dehydroabietyl succinate polyester.

Among them, DATE in the above figure is dehydroabietyl trimethylol propane ester; DSPE is dehydroabietyl succinate polyester.

detailed description

The present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited to the examples.

1. Preparation of trimethylolpropane dehydroabietate

The preparation method of a kind of rosin triol ester in the present invention is to take dehydroabietic acid and trimethylol propane as raw material, the dehydroabietic acid triol ester reaction that takes place in normal temperature under the presence of EDC/DMAP catalyst and organic solvent generates dehydroabietic acid triol Methyl propane ester, its reaction formula is as follows:

The main instruments and reagents used for the preparation of trimethylolpropane dehydroabietate are:

Instrument: rotary evaporator (Xihuayi (Beijing) Co., Ltd.)

The column diameter used in column chromatography is 60mm*30mm

Infrared spectrometer (Nicolet IS10)

High performance liquid chromatography (Agilent1260-HPLC)

LC/MS (Shimadzu LCMS-2010A)

NMR spectrometer (Bruker Avance(600/400)MHz spectrometer)

Gel permeation chromatography (Waters 1525 system)

Thermogravimetric analysis (STA449F3 Jupiter)

Reagent: dehydroabietic acid (self-made, weigh disproportionated rosin and add absolute ethanol to dissolve it and filter it with suction, add ethanolamine solution dropwise, add hot distilled water, extract with petroleum ether for many times, take the water layer, cool and crystallize naturally, suction filter, re- Crystallize multiple times, acidify, add hot distilled water, after cooling, filter under reduced pressure, wash to obtain the crude product of dehydroabietic acid, recrystallize multiple times, dry to obtain white dehydroabietic acid), trimethylolpropane ( Provided by Aladdin Reagent Co., Ltd.), EDC (provided by Aladdin Reagent Co., Ltd.), DMAP (provided by Aladdin Reagent Co., Ltd.), silica gel (industrial grade 100-200 mesh), succinic acid, p-toluenesulfonic acid, Sodium chloride, sodium carbonate, ethanol, methanol (chromatographically pure), tetrahydrofuran (chromatographically pure, AR), dichloromethane, petroleum ether, ethyl acetate and other unspecified reagents are analytically pure.

Example 1

A preparation method of trimethylolpropane dehydroabietic acid, using dehydroabietic acid and trimethylol propane as raw materials, the reaction is carried out in a water bath earlier, in a 250ml three-necked flask, feed nitrogen for 15 minutes, add Dehydroabietic acid (1eq, 1.5g, 0.005mol), trimethylolpropane (4.5eq, 3.015g, 0.024mol) and DMAP (4-dimethylaminopyridine) (1.6eq, 1g, 0.008mol), Dissolve in 20mL of N,N-dimethylformamide (DMF). After dissolving, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, and quickly add EDC (1-(3-dimethylaminopropyl base)-3-ethylcarbodiimide) (1.2eq, 1.15g, 0.006mol), continue to pass nitrogen gas, after 15 minutes of reaction, remove the ice cubes, seal each port with a plug, and place in water at room temperature at 25°C Carry out the reaction, stop stirring continuously for 24 hours, and the reaction is completed. The material obtained by the reaction is transferred to a single-necked flask for rotary steaming. The evaporator was rotary evaporated for 30 min, and DMF was removed to obtain a solid mixture.

The above solid mixture was dissolved in 25 mL of petroleum ether, washed with saturated brine, the organic layer was taken, and spin-dried under a rotary evaporator to obtain a viscous crude product of trimethylolpropane dehydroabietic acid.

The above crude product of trimethylolpropane dehydroabietate is subjected to column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. The adsorbent in the column chromatography process is silica gel, the eluent is petroleum ether/ethyl acetate system, and the dosage is 2000mL, which is 1/3 of the column volume.

It was measured that the conversion rate of dehydroabietic acid was 94%, the yield rate was 43.6%, and the purity measured by high performance liquid chromatography was 96.3%.

Example 2

A kind of preparation method of dehydroabietic acid trimethylol propane ester, take dehydroabietic acid and trimethylol propane as raw material, reaction is carried out in water bath earlier, in 250ml there-necked flask, feed nitrogen 15 minutes, dehydroabietic acid

(1eq, 1.5g, 0.005mol), trimethylolpropane (1.2eq, 0.8g, 0.006mol) and DMAP (4-dimethylaminopyridine) (1.6eq, 1g, 0.008mol), dissolved in 25mL After dissolving in tetrahydrofuran, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, and quickly add EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide) (1.2eq , 1.15g, 0.006mol), continue to blow nitrogen, after 20 minutes of reaction, remove the ice cubes, seal each port with a plug, react in water at room temperature 28 ° C, and stop stirring after 24 hours, the reaction is over, all The material was transferred to a single-necked flask and subjected to rotary evaporation using 80 mL of petroleum ether as a solvent on a rotary evaporator with a temperature of 40° C. and a pressure of 0.007 MPa for 45 minutes to remove tetrahydrofuran and obtain a solid mixture.

The above solid mixture was dissolved in 30 mL of ethanol, washed with saturated brine, the organic layer was taken, and spin-dried to obtain a viscous crude product of trimethylolpropane dehydroabietate.

The above crude product of trimethylolpropane dehydroabietate was obtained by column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. Wherein, during the column chromatography, the adsorbent is silica gel, and the eluent is petroleum ether/ethyl acetate system, and the dosage is 2400 mL, which is 2/5 of the column volume.

It was measured that the conversion rate of dehydroabietic acid was 76.8%, the yield rate was 24.3%, and the purity measured by high performance liquid chromatography was 95.7%.

Example 3

A kind of preparation method of dehydroabietic acid trimethylol propane ester, take dehydroabietic acid and trimethylol propane as raw material, reaction is carried out in water bath earlier, in 250ml there-necked flask, feed nitrogen 15 minutes, Add dehydroabietic acid (1 eq, 1.5 g, 0.005 mol), trimethylolpropane (4.5 eq, 3.015 g, 0.024 mol) and DMAP (4-dimethylaminopyridine) (1.6 eq, 1 g, 0.008 mol) , dissolved in 25mL of tetrahydrofuran, after dissolving, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, quickly add EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiethylene Amine) (1.2eq, 1.15g, 0.006mol), continue to pass nitrogen, after 25min of reaction, remove the ice cubes, seal each port with a stopper, react in water at room temperature 25°C, and stop stirring after 15h. After the reaction was completed, all the materials were transferred to a single-necked flask for rotary evaporation. The rotary evaporation used 150mL of petroleum ether as a solvent, and at a temperature of 50°C and a pressure of 0.007MPa, a rotary evaporator was used for rotary evaporation for 35 minutes to remove tetrahydrofuran. solid mixture.

The above solid mixture was dissolved in 30 mL of dichloromethane, washed with saturated brine, the organic layer was taken, and spin-dried to obtain a viscous crude product of trimethylolpropane dehydroabietate.

The above crude product of trimethylolpropane dehydroabietate was obtained by column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. Wherein, during the column chromatography, the adsorbent is silica gel, the eluent is petroleum ether/ethyl acetate system, and the dosage is 3000 mL, which is 1/2 of the column volume.

The measured conversion rate of dehydroabietic acid was 100%, the yield rate was 82%, and the purity measured by high performance liquid chromatography was 98.5%.

Example 4

A kind of preparation method of dehydroabietic acid trimethylol propane ester, take dehydroabietic acid and trimethylol propane as raw material, reaction is carried out in water bath earlier, in 250ml there-necked flask, feed nitrogen 15 minutes, Add dehydroabietic acid (1 eq, 1.5 g, 0.005 mol), trimethylolpropane (1 eq, 0.67 g, 0.005 mol) and DMAP (4-dimethylaminopyridine) (0.8 eq, 0.5 g, 0.004 mol) , dissolved in 18mL of tetrahydrofuran, after dissolving, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, quickly add EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiethylene Amine) (1.6eq, 1.50g, 0.008mol), continue to pass nitrogen, after 30 minutes of reaction, remove the ice cubes, seal each port with a stopper, react in water at room temperature 27 ° C, and keep stirring for 10 hours, the reaction is over , Transfer all the materials to a single-necked flask for rotary evaporation. The rotary evaporation uses 50 mL of petroleum ether as a solvent, and rotates for 40 minutes at a temperature of 45 ° C and a pressure of 0.007 MPa on a rotary evaporator to remove tetrahydrofuran and obtain a solid mixture.

The above solid mixture was dissolved in 30 mL of ethyl acetate, washed with saturated brine, the organic layer was taken, and spin-dried to obtain a viscous crude product of trimethylolpropane dehydroabietate.

The above crude product of trimethylolpropane dehydroabietate was obtained by column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. In the process of column chromatography, the adsorbent is silica gel, the eluent is petroleum ether/ethyl acetate system, and the dosage is 3000mL, which is 1/2 of the column volume.

It was measured that the conversion rate of dehydroabietic acid was 75.7%, the yield rate was 32.8%, and the purity measured by high performance liquid chromatography was 97.8%.

Example 5

A kind of preparation method of dehydroabietic acid trimethylol propane ester, take dehydroabietic acid and trimethylol propane as raw material, reaction is carried out in water bath earlier, in 250ml there-necked flask, feed nitrogen 15 minutes, Add dehydroabietic acid (1 eq, 1.5 g, 0.005 mol), trimethylolpropane (6 eq, 4.02 g, 0.03 mol) and DMAP (4-dimethylaminopyridine) (1.28 eq, 0.8 g, 0.0064 mol) , dissolved in 30mL of N,N-dimethylformamide, after dissolving, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, quickly add EDC (1-(3-dimethylaminopropyl) -3-Ethylcarbodiimide) (1.8eq, 1.725g, 0.009mol), continue to pass nitrogen gas, after half an hour of reaction, remove the ice cubes, seal each port with a plug, and conduct the reaction in water at room temperature 22°C React, and keep stirring for 20h; After the reaction is over, transfer all materials to a single-necked flask for rotary evaporation. The rotary evaporation uses 200mL of petroleum ether as a solvent, and the temperature is 50°C, and the pressure is 0.007MPa on a rotary evaporator. After steaming for 20 min, tetrahydrofuran was removed to obtain a solid mixture.

The above solid mixture was dissolved in 25 mL of petroleum ether, washed with saturated brine, the organic layer was taken, and spin-dried to obtain a viscous crude product of trimethylolpropane dehydroabietate.

The above crude product of trimethylolpropane dehydroabietate was obtained by column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. Wherein, during the column chromatography, the adsorbent is silica gel, the eluent is petroleum ether/ethyl acetate system, and the dosage is 2000 mL, which is 1/3 of the column volume.

It was measured that the conversion rate of dehydroabietic acid was 100%, the yield rate was 85.2%, and the purity measured by high performance liquid chromatography was 96.4%.

Example 6

A kind of preparation method of dehydroabietic acid trimethylol propane ester, take dehydroabietic acid and trimethylol propane as raw material, reaction is carried out in water bath earlier, in 250ml there-necked flask, feed nitrogen 10 minutes, Add dehydroabietic acid (1 eq, 1.5 g, 0.005 mol), trimethylolpropane (3 eq, 2.01 g, 0.016 mol) and DMAP (4-dimethylaminopyridine) (0.2 eq, 0.12 g, 0.001 mol) , dissolved in 25mL of dichloromethane, after dissolving, add a large amount of ice cubes to the water bath, cool the temperature to 0°C, quickly add EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodi imine) (1.5eq, 1.45g, 0.0075mol), continue to flow nitrogen, and after 20 minutes of reaction, remove the ice cubes, seal each port with a stopper, react in water at room temperature 18°C, and keep stirring for 24 hours; At the end, transfer all the materials to a single-necked flask for rotary evaporation. The rotary evaporation uses 100mL of petroleum ether as a solvent, and the temperature is 45°C and the pressure is 0.008MPa. mixture.

The above solid mixture was dissolved in 30 mL of ethanol, washed with saturated brine, the organic layer was taken, and spin-dried to obtain a viscous crude product of trimethylolpropane dehydroabietate.

The above crude product of trimethylolpropane dehydroabietate was obtained by column chromatography to obtain trimethylolpropane dehydroabietate in the form of white strip crystals. Wherein, during the column chromatography, the adsorbent is silica gel, the eluent is petroleum ether/ethyl acetate system, and the dosage is 3000 mL, which is 1/2 of the column volume.

It was measured that the conversion rate of dehydroabietic acid was 100%, the yield rate was 64%, and the purity was 98.1%.

2. Physicochemical properties, spectral data and structure determination of compounds

Infrared spectrometer (Nicolet IS10)

High performance liquid chromatography (Agilent1260-HPLC)

LC/MS (Shimadzu LCMS-2010A)

NMR spectrometer (Bruker Avance(600/400)MHz)

Gel permeation chromatography (Waters 1525 system)

Thermogravimetric analysis (STA449F3 Jupiter)

Instruments and equipment: measure infrared spectrum with Nicolet IS10 infrared spectrometer; nuclear magnetic resonance spectrum is measured with BrukerAvance (600/400) MHz nuclear magnetic resonance spectrometer, through detection and analysis of the product of embodiment 3, thereby determine the chemical structural formula of this compound.

The physical and chemical properties of the prepared compound: the appearance is white strip crystal; odorless; solubility: slightly soluble in water, completely soluble in ethanol, petroleum ether, dichloromethane and ethyl acetate organic solvents; its molecular formula is C ₂₆ H ₄₀ O ₄ ; molecular weight: 416.61.

From the infrared spectrogram of Fig. 1 dehydroabietic acid trimethylolpropane ester, it is known that the O-H stretching vibration peak occurs at 3427.48cm-1, and the bending vibration peak of O-H occurs at 1037.37cm-1; at 1723.69cm-1 The stretching vibration peak of C=O of the ester appears, and there is the stretching vibration peak of C-O at 1246.86cm-1, and there is no bending vibration peak of -OH in the carboxylic acid at 900-950cm-1, which proves that there is no -COOH in this system. In addition, 2928.74cm-1 is the stretching vibration peak of -CH3; the symmetrical -CH2 stretching vibration occurs at 1464.05cm-1 and 1497.88cm-1 and 1384.73cm-1 is the bending vibration peak of -CH3. The analysis by infrared spectrum showed that all dehydroabietic acid was converted into ester.

Fig. 2, the NMR spectrum of dehydroabietic acid trimethylolpropane ester (DATE), can be known by structure analysis attribution, 7.26ppm place is deuterated chloroform solvent peak, 6.89-7.17ppm three groups of peaks (two two Heavy peak, a single peak) splitting state is consistent with the position of the three hydrogens on the DATE benzene ring, the single peak at 4.20ppm, according to its displacement and the carbon on the ester bond (that is, carbon No. 26) Hydrogen matches, the quartet at 3.59ppm corresponds to the hydrogen on the carbon connected to the hydroxyl group (carbon No. 24, 25), and because the three groups of peaks at 6.89-7.17ppm correspond to the singlet at 4.20ppm The integral ratio of the quartet at 3.59ppm is exactly 1:1:1:2:4, which corresponds to the number of hydrogen atoms on the corresponding carbon, thereby further verifying that trimethylolpropane has been combined with dehydroabietic acid. In addition, the molecular weight of the compound was determined to be 416 by LC-MS, ¹ HNMR (399MHz, CDCl, ppm):, 7.17(d, J=8.1Hz, 1H; Ar), 7.01δ(d, J=8.7Hz, 1H; Ar), 6.89 (s, 1H; Ar), 4.20 (s, 2H, COOCH2), 3.59 (d, J = 11.3Hz, 2H; OCH2), 3.53 (d, J = 11.3Hz, 2H, OCH2), 2.95 -1.77(m,14H),1.59(s,H2O),1.30(s,1H),1.29(s,3H),1.28(s,1H),1.23(s,3H),1.22(s,6H), 0.87 (dd, J=9.3, 5.9 Hz, 3H). MS (ESI, m/z) for _C26H40O4 : ₄₁₇ (M ₊ ⁾ .

Fig. 3 is the carbon nuclear magnetic spectrogram of dehydroabietic acid trimethylol propane ester (DATE), as follows through measuring the signal of each carbon atom: 13CNMR (100MHz, CDCl , δ, ppm): 179.74 (17), 146.63(2), 145.75(5), 134.45(3), 126.94(4), 124.13(6), 123.99(1), 65.85(24), 65.83(25), 64.36(26), 48.09(8), 44.93(14), 43.00(23), 37.84(11), 36.98(13), 36.97(7), 33.42(18), 30.09(10), 25.33(15), 23.93(19,20), 22.53(16 ), 21.91(22), 18.55(9), 16.58(12), 7.37(21).

Fig. 4 is the thermogravimetric analysis diagram of the compound, through which the decomposition temperature of the compound can be obtained as 250-430°C.

Further determine that the name of this compound is trimethylolpropane dehydroabietate by the above analysis, and the chemical structural formula is as follows.

Further, the compounds prepared in Example 1, Example 2, Example 4, Example 5, and Example 6 were tested in the same way as the compound A prepared in Example 3, and the results obtained in all examples were the same as The infrared spectrum, hydrogen nuclear magnetic spectrum, carbon nuclear magnetic spectrum and thermogravimetric analysis diagram corresponding to compound A are highly consistent, indicating that the prepared product has excellent reproducibility.

The applicant further named the compound: dehydroabietic acid trimethylol propane ester.

It can be further confirmed that the English name of the compound is trimethylolpropanedehydroabietyate.

The applicant further confirmed that the decomposition temperature of this compound is 250-430°C.

Three, further illustrate the purposes of trimethylolpropane dehydroabietate in conjunction with the following examples, but the scope of protection is not limited to the following application examples.

Application Example 1

Weigh the dehydroabietic acid trimethylolpropane 0.01mol (4.2g) that embodiment 1 prepares, the succinic anhydride of 0.01mol (1g), the catalyst p-toluenesulfonic acid 0.2g, add successively the three-necked flask of 150mL In the process, add a water trap reflux condenser (connected to the dryer, a safety bottle, a vacuum pump) with a thermometer at 300 ° C, stop the nitrogen gas for 10 minutes, vacuumize, and repeat 3 times. Flow nitrogen, start heating, wait for the reactants to melt, turn on magnetic stirring, wait until the temperature rises to 120°C, maintain the temperature, stop nitrogen flow, vacuumize, keep the vacuum greater than 0.09Mpa, start timing reaction for 7 hours, and the reaction is over. Dissolve it in ethanol, put it in a dialysis bag with a molecular cut-off of 1000, and dialyze it with ethanol and water for 7 days respectively. Spin dry to obtain dehydroabietyl succinic acid polyester. The prepared dehydroabietylsuccinic acid polyester has good rigidity and thermal stability, and can be applied to adhesives and hot-melt coatings of pressure-sensitive and heat-sensitive adhesive tapes.

The obtained dehydroabietyl succinate polyester was a pale yellow solid. As measured by gel permeation chromatography, the number average molecular weight of the polymer was 3400, and the polydispersity was 1.2.

Application Example 2

Weigh the dehydroabietic acid trimethylol propane ester (DATE) 0.01mol (4.2g) that embodiment 3 prepares, the succinic acid (SA) of 0.01mol (1.18g), catalyst p-toluenesulfonic acid 0.2g , put into a 150mL three-necked flask in turn, add a water separator reflux condenser (connected to a dryer, a safety bottle, a vacuum pump) and a thermometer at 300°C, pass nitrogen gas for 10 minutes, stop nitrogen gas flow, vacuumize, and repeat 3 times. Flow nitrogen, start heating, wait for the reactants to melt, turn on magnetic stirring, wait until the temperature rises to 120°C, maintain the temperature, stop nitrogen flow, vacuumize, keep the vacuum greater than 0.09Mpa, start timing reaction for 7 hours, and the reaction is over. Dissolve it in ethanol, put it in a dialysis bag with a molecular cut-off of 1000, and dialyze it with ethanol and water for 7 days respectively. Spin dry to obtain dehydroabietyl succinic acid polyester. The prepared dehydroabietylsuccinic acid polyester has good rigidity and thermal stability, and can be applied to adhesives and hot-melt coatings of pressure-sensitive and heat-sensitive adhesive tapes.

The preparation of dehydroabietyl succinic acid polyester (DSPE), its reaction equation is:

The obtained dehydroabietyl succinate polyester was a pale yellow solid. As measured by gel permeation chromatography, the number average molecular weight of the polymer was 5215, and the polydispersity was 1.33.

The above-mentioned dehydroabietylsuccinic acid polyester (DSPE) is subjected to infrared detection, and the infrared spectrum obtained by detection is shown in Figure 5. In Fig. 5, the infrared spectrogram of dehydroabietic acid base succinic acid polyester (DSPE), compared with the infrared spectrogram of accompanying drawing 1 dehydroabietic acid trimethylol propane, the hydroxyl peak of 3440 disappears in the DSPE figure , the carbonyl peak also shifted relatively, it is speculated that the hydroxyl group participated in the esterification reaction and generated a new ester.

The above-obtained dehydroabietylsuccinic acid polyester (DSPE) is subjected to hydrogen nuclear magnetic spectrum detection, and the detected hydrogen nuclear magnetic spectrum is shown in Figure 6. Figure 6. In the DSPE NMR diagram, the results of the measurement are as follows. After analysis, it is known that the hydrogen atom peak adjacent to the hydroxyl group C disappears, and at the same time, the hydrogen adjacent to the ester group C increases, and the H newly connected to succinic acid also corresponds. Appeared, and the integral result was consistent with the theoretical number of H atoms, which further proved the occurrence of esterification reaction. 1HNMR (600MHz, CDCl3) δ7.15(d, J=8.2Hz, 1H, Ar), 7.00(d, J=8.1Hz, 1H, Ar), 6.87(s, 1H, Ar), 4.20-3.75(m ,6H,COOCH2),2.81-1.75(m,18H),1.56(s,H2O),1.48-1.26(d,J＝8.9Hz,2H),1.24–1.18(m,9H),0.87(t,J =7.4Hz, 3H).

Figure 7 is the thermogravimetric analysis of the polymer, and its decomposition temperature is 350-500°C.

Further confirm that the name of this compound is dehydroabietyl succinic acid polyester by above analysis.

Application Example 3

Weigh the dehydroabietic acid trimethylol propane ester 0.01mol (4.2g) that embodiment 3 prepares, the malonic acid of (0.42g), catalyst p-toluenesulfonic acid 0.2g, add in the three-necked flask of 150mL successively , add a water separator reflux condenser (connected to the dryer, safety bottle, vacuum pump) with a thermometer at 300°C, pass nitrogen gas for 10 minutes, stop nitrogen gas flow, vacuumize, and repeat 3 times. Flow nitrogen, start heating, wait for the reactants to melt, turn on magnetic stirring, wait until the temperature rises to 120°C, maintain the temperature, stop nitrogen flow, vacuumize, keep the vacuum greater than 0.09Mpa, start timing reaction for 7 hours, and the reaction is over. Dissolve it in ethanol, put it in a dialysis bag with a molecular cut-off of 1000, and dialyze it with ethanol and water for 7 days respectively. Spin dry to obtain dehydroabietyl malonate polyester.

The resulting dehydroabietylmalonate polyester was a white solid. Measured by gel permeation chromatography, the number-average molecular weight of the polymer is 3892, the polydispersity is 1.56, and the decomposition temperature is 320-480°C by thermogravimetric analysis.

The prepared dehydroabietyl malonate polyester, similar to dehydroabietyl succinate, has good rigidity and thermal stability, and can be used as an adhesive and heat-soluble adhesive for pressure-sensitive and heat-sensitive adhesive tapes coating.

Application Example 4

Weigh 0.01mol (4.2g) of dehydroabietyl trimethylolpropane ester and catalyst KOH 0.003mol (0.168g) in Example 5 and add them to the autoclave and start to heat up. When the temperature reaches 70°C, vacuumize with a vacuum pump When the gauge pressure is around -0.05MPa, _N2 is purged and replaced, and the vacuum is pumped for 30 minutes. Then, when the temperature is 130±5°C, start to add ethylene oxide (EO) intermittently, and the pressure of the reactor is controlled at 0.2-0.4 MPa. After the feeding is completed, when the pressure of the reactor drops, continue to react at this temperature until it drops to -0.05 MPa at the beginning, and the reaction is complete at this time, and polydehydroabietyl ether is obtained.

Dissolve the crude product and the catalyst KOH in water three times and add a small amount of acetic acid dropwise, and filter with a filter to remove impurities and insoluble matter. The resulting sample was extracted with dichloromethane, the extract was removed by rotary evaporation and then vacuum-dried at 65°C for 24 hours to obtain dehydroabietic polyether. Rosin is non-toxic and can be used as medicine. The polyether and the medicine are combined by hydrogen bonds and can be used as a pharmaceutical carrier. Because the substance is amphiphilic, it can be used as a surfactant.

Application Example 5

Weigh the dehydroabietic acid ester 0.01mol (4.2g) that embodiment 1 prepares, the dodecanoic acid (lauric acid) of 0.024mol (4.8g), catalyst p-toluenesulfonic acid 0.45g, add successively the three-necked flask of 250mL In the process, add a water trap reflux condenser (connected to the dryer, a safety bottle, a vacuum pump) with a thermometer at 300 ° C, stop the nitrogen gas for 10 minutes, vacuumize, and repeat 3 times. Flow nitrogen, start heating, wait for the reactants to melt, turn on magnetic stirring, wait until the temperature rises to 120°C, maintain the temperature, stop nitrogen flow, vacuumize, keep the vacuum greater than 0.09Mpa, start timing reaction for 7 hours, and the reaction is over. Dissolve it in ethanol, put it in a dialysis bag with a molecular cut-off of 500, and dialyze it with ethanol and water for 7 days. Spin dry to obtain dehydroabietyl dilaurate. The product is similar in structure to the commonly used plasticizer octyl phthalate, and its good cold resistance and environmental protection and non-toxic characteristics, dehydroabietyl dilaurate series products are used as environmentally friendly plasticizers and improved The plasticizing agent used in PVC has a plasticizing effect and has good practical application value.

Claims (10)

1. Colophonium three alcohol ester, it is characterised in that: the chemical name of described Colophonium three alcohol ester is: dehydroabietic acid trihydroxy methyl third Alkyl ester, its chemical structural formula is:

This compound outward appearance is white bar shaped crystal；Tasteless；Dissolubility: be slightly soluble in water, is completely dissolved in ethanol, petroleum ether, dichloro Methane and ethyl acetate organic solvent；Decomposition temperature: 250-430 DEG C；Its molecular formula is C₂₆H₄₀O₄；Molecular weight is: 416.61.

2. the preparation method of Colophonium three alcohol ester as claimed in claim 1, it is characterised in that: the preparation of this Colophonium three alcohol ester It is with dehydroabietic acid and trimethylolpropane as raw material, with EDC/DMAP as catalyst, occurs with under room temperature in organic solvent Esterification synthesis dehydroabietic acid trihydroxymethylpropanyl ester, reaction equation is:

Dehydroabietic acid trimethylolpropane dehydroabietic acid trihydroxymethylpropanyl ester.

A kind of preparation method of Colophonium three alcohol ester, it is characterised in that: reactant discussed above material Mass ratio be: dehydroabietic acid: trimethylolpropane: DMAP:EDC=1.5:0.67～4.02:0.12～1:1.15～1.725.

A kind of preparation method of Colophonium three alcohol ester, it is characterised in that: described organic solvent is two Any one in chloromethanes, oxolane and N,N-dimethylformamide.

5. the preparation method of a kind of Colophonium three alcohol ester as described in any one of claim 2-4, it is characterised in that: the method concrete Step includes:

1) add material to react: in the reaction vessel having got rid of oxygen, add dehydroabietic acid and trimethylolpropane Raw material, and add DMAP, any one is organic molten to dissolve them in dichloromethane or oxolane or DMF Agent, its consumption is: dehydroabietic acid: organic solvent=1g:12～20mL, and after dissolving, cooling makes temperature be cooled to 0 DEG C, rapidly joins EDC, starvation, after reaction 15～30min, recover room temperature and continue reaction, stop after being stirred continuously 10～24h, reaction terminates, Above-mentioned reacted material carries out rotation steam, remove solvent, obtain solid mixture；

2) obtain crude product: dissolved by above-mentioned solid mixture solvent, and wash with saturated aqueous common salt, take organic layer, be spin-dried for, Obtain dehydroabietic acid trihydroxymethylpropanyl ester crude product；

3) purification of product: by above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product by the i.e. available white of column chromatography for separation The compound of bar shaped lenticular, confirms as dehydroabietic acid trihydroxymethylpropanyl ester through structured testing.

A kind of preparation method of Colophonium three alcohol ester, it is characterised in that: described 2) in solvent be Any one in petroleum ether, ethanol, dichloromethane and ethyl acetate.

A kind of preparation method of Colophonium three alcohol ester, it is characterised in that: described rotation steaming be with 50～ 200mL petroleum ether is solvent, and being 40～50 DEG C in temperature is that 0.007～0.009MPa backspin steams 20～45min with pressure.

A kind of preparation method of Colophonium three alcohol ester, it is characterised in that: described column chromatography is silicon Plastic column chromatography, adsorbent used is silica gel, and eluant is petrol ether/ethyl acetate system, consumption be pillar volume 2/1 ~ 3/1。

9. according to the preparation method of Colophonium three alcohol ester a kind of described in any one of claim 6-8, it is characterised in that: the party's legal system The standby dehydroabietic acid trihydroxymethylpropanyl ester obtained, records high purity more than 95.5% by high performance liquid chromatography.

10. the application of Colophonium three alcohol ester described in claim 1, it is characterised in that: Colophonium three alcohol ester can be applicable to pressure-sensitive and hot The binding agent of sensitive adhesive tape, the plasticizer of resin and modifying agent, hot melt coating, surfactant and pharmaceutical carrier.