CN104693024A - Rosin triol ester as well as preparation method and application thereof - Google Patents
Rosin triol ester as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a rosin triol ester and a preparation method therefore. The chemical name of the rosin triol ester is trimethylolpropane dehydroabietyate. The preparation method of the rosin triol ester comprises the following steps: by taking dehydroabietic acid and trimethylolpropane as the raw materials, EDC/DMAP as the catalysts, and any one of methylene chloride, tetrahydrofuran and N,N-dimethyl formamide as the solvent, performing an esterification reaction at normal temperature to synthesize the trimethylolpropane dehydroabietyate. The esterification method is completed in one step; the steric hindrance can be effectively overcome; the yield is high; the reaction is performed at room temperature so that the energy consumption can be reduced; the byproducts are soluble in water and easy to purify; the smell is light and few three wastes are generated; and the solvent selection range is wide. The ester prepared by use of the method is wide in use, and can be used as plasticizers and modifiers of various resins, excellent adhesives for pressure-sensitive and thermosensitive adhesive tapes, hot melt coatings, surface activators and pharmaceutical vectors.
Description
Technical field
The present invention relates to rosin spirit deep process technology field, especially a kind of rosin three alcohol ester and its preparation method and application.
Background technology
Rosin is a kind of natural resin, and raw material comes from reproducible pine forest resource, is one of most important product in China's chemistry of forest product industry.China's rosin annual production more than 80 ten thousand tons, be one of rosin main exit country, account for 60% of volume of world trade, most of developed countries rosin is all dependence on import.The main component of rosin is resinous acid, accounts for total mass 85% ~ 90%, and they are monocarboxylic acids respectively having two double bonds that a class has the luxuriant and rich with fragrance skeleton of three rings.Rosin has unique chemical structure makes it have excellent environmental friendliness characteristic, as anticorrosion, moistureproof, insulation, bonding, emulsification, softens.Rosin and derivative thereof are widely used in pigment, varnish, ink, paper shaping; Simultaneously also be applied to chewing gum, pesticide industry, electronic industry, in dental field and cosmetic industry.At present, the synthesis of rosinyl polymkeric substance becomes the focus of research both at home and abroad.Researchist has successfully prepared multiple colophony based functional polymkeric substance and has been applied to the every field such as medicine, coated material, foodstuff additive, chemical industry catalysis, environment protection and fractionation by adsorption.And the carboxyl of rosin is positioned on tertiary carbon atom, greatly sterically hindered, severe reaction conditions is existing problems general in rosin esterification process.Find relevant rosin esterification method at present and mainly contain following 3 kinds: Protic Acid Catalyzed method, solid acid catalysis method and acyl chloride esterification method.
Protonic acid is the custom catalysts of alcoholic acid esterification, effective equally for rosin esterification.In reaction, protonic acid is first by protonated for the carbonyl of resinous acid, makes it than being easier to and alcohol generation nucleophilic addition(Adn), then prototropy, eliminates water molecules, then eliminates proton, forms ester (SN2 mechanism).Conventional protonic acid mainly contains sulfuric acid, phosphoric acid, Hypophosporous Acid, 50, boric acid, Phenylsulfonic acid and P-TOLUENE SULFO ACID 99 etc.The method has the advantages such as catalyst source is wide, cheap and easy to get, excellent catalytic effect, but there is the shortcomings such as etching apparatus, catalyzer and product separation difficulty, is substituted by other method aborning at present.
Solid acid catalysis method is by means of the acidic substance of solid surface to promote the material of chemical reaction, its catalytic mechanism and protonic acid similar.Conventional solid acid is mainly Zn
2+class solid acid, as ZnO, ZnCl
2:, ZnS0
4, Zn (OAC)
2deng.Solid acid catalysis method has not etching apparatus, easily separated, can reuse advantage, but need heating, product easily oxidized, the defect such as darken.
Acyl chloride esterification method first changes the resinous acid of rosin into acyl chlorides, and acyl chlorides again alcoholysis obtains corresponding ester, and conventional acyl chlorides reagent has the thionyl chloride (SOCl of brand-new
2), oxalyl chloride (C
2o
2cl
2), phosgene (COCl
2) etc.Acyl chloride esterification method, mild condition, productive rate is higher; But its shortcoming need carry out strict control to reaction conditions when preparing acyl chlorides, not easily eliminates excessive SOCl
2,serious to equipment corrosion religion, and acyl chlorides needs now-making-now-using, keeps anhydrous drying, and condition is harsh, stepwise reaction, length consuming time.
For above-mentioned several rosin esterification method Problems existing, Steglich esterification process is incorporated in rosin esterification process by the present invention.
The main component of rosin is resinous acid, and common resinous acid can be divided into abietic type acid, pimaric acid and isopimaric acid type resinous acid and laudanum type resinous acid according to the difference of alkyl and position of double bond.Wherein abietic acid is the main component of natural resin rosin, and content is 45%-54%, and abietic acid has the luxuriant and rich with fragrance skeleton structure of three rings, has conjugated double bond and multiple chiral carbon atom, and contains carboxyl and a sec.-propyl of hydrophilic radical.Due to the conjugated double bond containing higher-energy in abietic acid, cause rosin character extremely unstable, easily generated dark colour Vinsol by the oxygen oxidation in air.If in order to the unstable structure changing yoke double bond, abietic acid has and is generated as phenyl ring by disproportionation reaction dehydrogenation or hydrogenation removes the trend that double bond is converted into metastable form.
The present invention generates a kind of new rosin three alcohol ester by with dehydroabietic acid and TriMethylolPropane(TMP) for raw material passes through Steglich esterification process, and this material not yet has report up till now.
Summary of the invention
The object of the invention is to provide a kind of rosin three alcohol ester and its preparation method and application, and the present invention is for raw material prepares dehydroabietic acid trihydroxymethylpropanyl ester by Steglich esterification process with dehydroabietic acid and TriMethylolPropane(TMP).Steglich esterification process refers to that EDC-DMAP is as catalyzer, at room temperature, effectively overcomes reactant sterically hindered, synthetic ester.Steglich esterification process, the method one step completes, and effectively overcome sterically hindered, productive rate is high, reacts under room temperature, reduces energy consumption, and water-soluble being easy to of by product is purified, and the little three wastes of smell are few, and solvent range of choice is wide, avoids the Problems existing of above-mentioned esterification process.The dehydroabietic acid trihydroxymethylpropanyl ester that the present invention prepares has a wide range of applications.
For realizing above object, the technical solution used in the present invention is:
First object of the present invention is for providing a kind of new compound: rosin three alcohol ester.
A kind of rosin three alcohol ester, the chemical name of this compound is: dehydroabietic acid trihydroxymethylpropanyl ester, and its chemical structural formula is:
This compound outward appearance is white bar shaped crystal; Tasteless; Solvability: be slightly soluble in water, is dissolved in ethanol, sherwood oil, methylene dichloride and ethyl acetate organic solvent completely; Decomposition temperature: 250-430 DEG C; Its molecular formula is C
26h
40o
4;molecular weight is: 416.61.
The English name of this compound is: trimethylolpropane dehydroabietyate.
Above compound, applicant does not find same structure and the identical material of physicochemical property at present.
The present invention's second object is to provide a kind of preparation method of rosin three alcohol ester.
The preparation method of rosin three alcohol ester: being with dehydroabietic acid and TriMethylolPropane(TMP) for a raw material, take EDC/DMAP as catalyzer, in organic solvent with under normal temperature esterification synthesis dehydroabietic acid trihydroxymethylpropanyl ester occurs, reaction formula is:
The mass ratio of above-described reaction mass is: dehydroabietic acid: TriMethylolPropane(TMP): DMAP:EDC=1.5:0.67 ~ 4.02:0.12 ~ 1:1.15 ~ 1.725.
Described EDC is a water-soluble carbodiimide, is used as the activating reagent of carboxyl in the esterification reaction, makes carboxylic acid and alcohol generation esterification in organic chemistry with EDC and catalyzer DMAP (DMAP).EDC just plays the effect of activated carboxyl in reaction process, and what play katalysis is that DMAP, EDC amount of substance is greater than dehydroabietic acid amount of substance, can completely by the effect activated to reach carboxyl.
The above organic solvent is any one in methylene dichloride, tetrahydrofuran (THF) and DMF.
Wherein said DMAP chemical name is DMAP, and EDC chemical name is 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide.
Preparation method's concrete steps of the above a kind of rosin three alcohol ester comprise:
1) add material to react: getting rid of in the reaction vessel of oxygen, add dehydroabietic acid and TriMethylolPropane(TMP) raw material, and add DMAP (DMAP), they are dissolved in methylene dichloride or tetrahydrofuran (THF) or N, any one organic solvent of dinethylformamide, its consumption is: dehydroabietic acid: organic solvent=1g:12 ~ 20mL, after dissolving, cooling makes temperature be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) fast, starvation, after reaction 15 ~ 30min, recover normal temperature and continue reaction, stop after continuous stirring 10-24h, reaction terminates, above-mentioned reacted material is carried out revolving steaming, except desolventizing, obtain solid mixture,
2) preparation of crude product: by above-mentioned solid mixture dissolution with solvents, and use saturated common salt water washing, get organic layer, be spin-dried for, obtains dehydroabietic acid trihydroxymethylpropanyl ester crude product;
3) purification of product: the compound that above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product can be obtained white bar shaped lenticular by column chromatography for separation, confirms as dehydroabietic acid trihydroxymethylpropanyl ester through structured testing.
Further, described step 1) normal temperature be 15 ~ 30 DEG C, be preferably 20 ~ 28 DEG C.
Further, described stirring is carried out the reaction times and is preferably 14 ~ 18h.
Described step 2) solvent be selected from sherwood oil, ethanol, methylene dichloride and ethyl acetate any one.
Described eliminating oxygen and starvation can realize by passing into the rare gas elementes such as nitrogen, argon gas, helium.
Described revolve that to steam solvent used be sherwood oil, consumption is 50 ~ 200mL.
Described temperature of revolving steaming is 40 ~ 50 DEG C, and pressure is 0.007 ~ 0.009MPa, and revolving the steaming time is 20 ~ 45min.
Described column chromatography is silica gel column chromatography.
Described column chromatography sorbent material used is silica gel.
Described column chromatography eluent is petrol ether/ethyl acetate system, and consumption is 2/1 ~ 3/1 of pillar volume.
Further, the dehydroabietic acid trihydroxymethylpropanyl ester that the method prepares, records high purity more than 95.5% by high performance liquid chromatography.
In the present invention, the 3rd object is the purposes providing rosin three alcohol ester:
In the present invention, rosin three alcohol ester is a kind of new rosin alcohol, dehydroabietic acid trihydroxymethylpropanyl ester is with two-OH functional groups, tool has been widely used, can be used for polycondensation synthesizing polyester etc., such as with diacid polycondensation synthesizing amphipathic polycondensate, the tackiness agent of good pressure-sensitive and heat-sensitive glue adhesive tape can be formed; Have condense many finger rings rigid structure because rosin three alcohol ester contains dehydroabietic acid group again, there is good thermotolerance, can be used for softening agent and the properties-correcting agent of various kinds of resin, as for ethyl cellulose, chlorinated rubber, as softening agent in Vinylite and the obtained varnish of Nitrocellulose, it is together with various filmogen, its character can be made to improve, as with water-soluble, film-forming material, casein and zein mixing improve its adhesion and colour stability; Time together with water-insoluble filmogen, the tackiness agent of good pressure-sensitive and heat-sensitive glue adhesive tape can be formed; And thermally melting coating etc. can be formed time together with ethyl cellulose, vinyl polymer.Also serial ether derivative be can form, as can hydroxy polyethers be formed with epoxide reaction, tensio-active agent or pharmaceutical carrier can be used as.
The beneficial effect that the present invention obtains:
1. the invention provides a kind of novel compound rosin three alcohol ester, the chemical name of this compound is dehydroabietic acid trihydroxymethylpropanyl ester.This invention utilizes renewable resources rosin to prepare dehydroabietic acid trihydroxymethylpropanyl ester for main raw material, raw materials cost is low, wide material sources, non-renewable petrochemicals can be replaced, safe preparation process, nontoxic, expand China's Gum Rosin Industry, and rosin three alcohol ester prepared has biodegradability, environmental friendliness.
2. the dehydroabietic acid trihydroxymethylpropanyl ester prepared is compared with dehydroabietic acid monoglyceride, and three hydroxyls are in space equivalence, and compound with regular structure, does not exist isomers.
3. invention introduces Steglich esterification process, this esterification process, a step completes, effectively overcome sterically hindered, productive rate is high, reacts under room temperature, reduces energy consumption, water-soluble being easy to of by product is purified, the little three wastes of smell are few, and solvent range of choice is wide, overcomes the problem that Protic Acid Catalyzed method, solid acid esterification process and acyl chloride esterification method are deposited, present method can be used for efficiently preparing rosin three alcohol ester, the dehydroabietic acid trihydroxymethylpropanyl ester high purity more than 95.5% that the inventive method prepares.
4. make catalyzer with EDC/DMAP, effectively overcome sterically hindered, compared with chloride method, a step completes reaction, and productive rate is high, and toxicity is lower, and solvent range of choice is wide, and condition milder, easily purifies.
5. revolve and steam compared with common underpressure distillation, which increase distillation area.Therefore can shorten distillation time, and not need to add zeolite, can better distill.
6. the dehydroabietic acid trihydroxymethylpropanyl ester prepared is with two-OH functional groups, and tool has been widely used, and can be used for polycondensation synthesizing polyester etc., such as, with diacid polycondensation synthesizing amphipathic polycondensate, can form the tackiness agent of good pressure-sensitive and heat-sensitive glue adhesive tape.
7. have condense many finger rings rigid structure because rosin three alcohol ester introduces dehydroabietic acid group, there is good thermotolerance, can be used for softening agent and the properties-correcting agent of various kinds of resin, as for ethyl cellulose, chlorinated rubber, as softening agent in Vinylite and the obtained varnish of Nitrocellulose, it is together with various filmogen, its character can be made to improve, as with water-soluble, film-forming material, casein and zein mixing improve its adhesion and colour stability; Time together with water-insoluble filmogen, the tackiness agent of good pressure-sensitive and heat-sensitive glue adhesive tape can be formed; And thermally melting coating etc. can be formed time together with ethyl cellulose, vinyl polymer.Also can form serial ether derivative, as can hydroxy polyethers be formed with epoxide reaction, can be used as the use of surfactant materials or medicinal medicine carrying.
Accompanying drawing explanation
Fig. 1 is dehydrogenation fir base trihydroxymethylpropanyl ester infrared spectrum
Fig. 2 is dehydrogenation fir base trihydroxymethylpropanyl ester hydrogen nuclear magnetic resonance spectrogram
Fig. 3 is the carbon-13 nmr spectra figure of dehydrogenation fir base trihydroxymethylpropanyl ester.
Fig. 4 is the thermogravimetric analysis figure of dehydrogenation fir base trihydroxymethylpropanyl ester
Fig. 5 is the Infrared Characterization collection of illustrative plates of dehydrogenation fir base succinic acid polyester.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of dehydrogenation fir base succinic acid polyester.
Fig. 7 is the thermogravimetric analysis figure of dehydrogenation fir base succinic acid polyester.
Wherein in above-mentioned figure, DATE is dehydrogenation fir base trihydroxymethylpropanyl ester; DSPE is dehydrogenation fir base succinic acid polyester.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but protection scope of the present invention is not limited only to embodiment.
One, the preparation of dehydroabietic acid trihydroxymethylpropanyl ester
In the present invention, a kind of preparation method of rosin three alcohol ester is with dehydroabietic acid and TriMethylolPropane(TMP) for raw material, the dehydroabietic acid trihydroxymethylpropanyl ester that normal temperature generation esterification generates under EDC/DMAP catalyzer and organic solvent exist, and its reaction formula is as follows:
Prepare dehydroabietic acid trihydroxymethylpropanyl ester key instrument used and reagent is:
Instrument: Rotary Evaporators (westernization instrument (Beijing) company limited)
Pillar diameter used by column chromatography is 60mm*30mm
Infrared spectrometer (Nicolet IS10)
High performance liquid chromatography (Agilent1260-HPLC)
LC-MS (Shimadzu LCMS-2010A)
Nuclear magnetic resonance spectrometer (Bruker Avance (600/400) MHz spectrometer)
Gel permeation chromatography (Waters 1525 system)
Thermogravimetric analysis (STA449F3 Jupiter)
Reagent: dehydroabietic acid (self-control, take disproportionation rosin and add anhydrous alcohol solution suction filtration, after dripping ethanolamine solutions, add hot distilled water, repeatedly extract with sherwood oil, water intaking layer, natural cooling crystallization, suction filtration, recrystallization repeatedly, acidifying, add hot distilled water, after cooling, decompress filter, washing, after dehydroabietic acid crude product, recrystallization repeatedly after, dry, obtain white dehydroabietic acid), TriMethylolPropane(TMP) (company limited provides by Aladdin reagent), EDC (company limited provides by Aladdin reagent), DMAP (company limited provides by Aladdin reagent), silica gel (technical grade 100-200 order), succinic acid, tosic acid, sodium-chlor, sodium carbonate, ethanol, methyl alcohol (chromatographically pure), tetrahydrofuran (THF) (chromatographically pure, AR), methylene dichloride, sherwood oil, ethyl acetate and other undeclared reagent are for being analytical pure.
Embodiment 1
A kind of preparation method of dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, pass into nitrogen 15 minutes, add dehydroabietic acid (1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (4.5eq, 3.015g, 0.024mol) with DMAP (4-dimethylaminopyridine) (1.6eq, 1g, 0.008mol), be dissolved in the N of 20mL, in dinethylformamide (DMF), after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.2eq fast, 1.15g, 0.006mol), continue logical nitrogen, after reaction 15min, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 25 DEG C reacts, stop after continuous stirring 24h, reaction terminates, the material be obtained by reacting is transferred in single port flask and carry out revolving steaming, it is described that to revolve steaming be for solvent with 100mL sherwood oil, it is 45 DEG C in temperature, pressure be 0.008MPa rotatory evaporator on revolve steam 30min, removing DMF, obtain solid mixture.
By above-mentioned solid mixture 25mL petroleum ether dissolution, saturated common salt water washing, gets organic layer, is spin-dried under Rotary Evaporators, obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
By above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product by column chromatography, white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester can be obtained.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 2000mL is 1/3 of column volume.
Recording dehydroabietic acid transformation efficiency is 94%, and productive rate is 43.6%, and recording purity by high performance liquid chromatography is 96.3%.
Embodiment 2
A preparation method for dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl third for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, passes into nitrogen 15 minutes, adds dehydroabietic acid
(1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (1.2eq, 0.8g, 0.006mol) with DMAP (4-dimethylaminopyridine) (1.6eq, 1g, 0.008mol), be dissolved in the tetrahydrofuran (THF) of 25mL, after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.2eq fast, 1.15g, 0.006mol), continue logical nitrogen, after reaction 20min, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 28 DEG C reacts, and stop after constantly stirring 24h, reaction terminates, all materials are transferred in single port flask and carry out revolving steaming, it is described that to revolve steaming be for solvent with 80mL sherwood oil, it is 40 DEG C in temperature, pressure be 0.007MPa rotatory evaporator on revolve steam 45min, removing tetrahydrofuran (THF), obtain solid mixture.
By above-mentioned solid mixture 30mL dissolve with ethanol, saturated common salt water washing, gets organic layer, is spin-dried for, and obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
Above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product is obtained white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester by column chromatography.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 2400mL is 2/5 of column volume.
Recording dehydroabietic acid transformation efficiency is 76.8%, and productive rate is 24.3%, and recording purity by high performance liquid chromatography is 95.7%.
Embodiment 3
A kind of preparation method of dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl third for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, pass into nitrogen 15 minutes, add dehydroabietic acid (1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (4.5eq, 3.015g, 0.024mol) with DMAP (4-dimethylaminopyridine) (1.6eq, 1g, 0.008mol), be dissolved in the tetrahydrofuran (THF) of 25mL, after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.2eq fast, 1.15g, 0.006mol), continue logical nitrogen, after reaction 25min, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 25 DEG C reacts, and stop after constantly stirring 15h, reaction terminates, all materials are transferred in single port flask and carry out revolving steaming, it is described that to revolve steaming be for solvent with 150mL sherwood oil, it is 50 DEG C in temperature, pressure be 0.007MPa rotatory evaporator on revolve steam 35min, removing tetrahydrofuran (THF), obtain solid mixture.
Dissolved by above-mentioned solid mixture 30mL methylene dichloride, saturated common salt water washing, gets organic layer, is spin-dried for, and obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
Above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product is obtained white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester by column chromatography.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 3000mL is 1/2 of column volume.
Recording dehydroabietic acid transformation efficiency is 100%, and productive rate is 82%, and recording purity by high performance liquid chromatography is 98.5%.
Embodiment 4
A kind of preparation method of dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl third for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, pass into nitrogen 15 minutes, add dehydroabietic acid (1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (1eq, 0.67g, 0.005mol) with DMAP (4-dimethylaminopyridine) (0.8eq, 0.5g, 0.004mol), be dissolved in the tetrahydrofuran (THF) of 18mL, after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.6eq fast, 1.50g, 0.008mol), continue logical nitrogen, after reaction 30min, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 27 DEG C reacts, and constantly stir 10h, reaction terminates, all materials are transferred to row in single port flask and revolve steaming, it is described that to revolve steaming be for solvent with 50mL sherwood oil, it is 45 DEG C in temperature, pressure be 0.007MPa rotatory evaporator on revolve steam 40min, removing tetrahydrofuran (THF), obtain solid mixture.
By above-mentioned solid mixture 30mL acetic acid ethyl dissolution, saturated common salt water washing, gets organic layer, is spin-dried for, and obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
Above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product is obtained white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester by column chromatography.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 3000mL is 1/2 of column volume.
Recording dehydroabietic acid transformation efficiency is 75.7%, and productive rate is 32.8%, and recording purity by high performance liquid chromatography is 97.8%.
Embodiment 5
A kind of preparation method of dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl third for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, pass into nitrogen 15 minutes, add dehydroabietic acid (1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (6eq, 4.02g, 0.03mol) with DMAP (4-dimethylaminopyridine) (1.28eq, 0.8g, 0.0064mol), be dissolved in 30mL N, in dinethylformamide, after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.8eq fast, 1.725g, 0.009mol), continue logical nitrogen, after reacting half an hour, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 22 DEG C reacts, and constantly stir 20h, reaction terminates, and is transferred to by all materials in single port flask and carries out revolving steaming, described in revolve steaming be with 200mL sherwood oil for solvent, be 50 DEG C in temperature, pressure be 0.007MPa rotatory evaporator on revolve and steam 20min, removing tetrahydrofuran (THF), obtains solid mixture.
By above-mentioned solid mixture 25mL petroleum ether dissolution, saturated common salt water washing, gets organic layer, is spin-dried for, and obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
Above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product is obtained white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester by column chromatography.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 2000mL is 1/3 of column volume.
Recording dehydroabietic acid transformation efficiency is 100%, and productive rate is 85.2%, and recording purity by high performance liquid chromatography is 96.4%.
Embodiment 6
A kind of preparation method of dehydroabietic acid trihydroxymethylpropanyl ester, with dehydroabietic acid and trishydroxymethyl third for raw material, reaction is first carried out in water-bath, in 250ml there-necked flask, pass into nitrogen 10 minutes, add dehydroabietic acid (1eq, 1.5g, 0.005mol), TriMethylolPropane(TMP) (3eq, 2.01g, 0.016mol) with DMAP (4-dimethylaminopyridine) (0.2eq, 0.12g, 0.001mol), be dissolved in 25mL methylene dichloride, after dissolving, a large amount of ice cube is added in water-bath, temperature is made to be cooled to 0 DEG C, add EDC (1-(3-dimethylamino-propyl)-3-ethyl carbodiimide) (1.5eq fast, 1.45g, 0.0075mol), continue logical nitrogen, after reaction 20min, ice cube is removed, with stopper each mouth good seal, in water, normal temperature 18 DEG C reacts, and constantly stir 24h, reaction terminates, and is transferred to by all materials in single port flask and carries out revolving steaming, described in revolve steaming be with 100mL sherwood oil for solvent, be 45 DEG C in temperature, pressure be 0.008MPa rotatory evaporator on revolve and steam 30min, removing tetrahydrofuran (THF), obtains solid mixture.
By above-mentioned solid mixture 30mL dissolve with ethanol, saturated common salt water washing, gets organic layer, is spin-dried for, and obtains thick dehydroabietic acid trihydroxymethylpropanyl ester crude product.
Above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product is obtained white bar shaped lenticular dehydroabietic acid trihydroxymethylpropanyl ester by column chromatography.Wherein in column chromatography procedure, sorbent material is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 3000mL is 1/2 of column volume.
Recording dehydroabietic acid transformation efficiency is 100%, and productive rate is 64%, and purity is 98.1%.
Two, the physico-chemical property of compound, spectral data and structure are determined
Infrared spectrometer (Nicolet IS10)
High performance liquid chromatography (Agilent1260-HPLC)
LC-MS (Shimadzu LCMS-2010A)
Nuclear magnetic resonance spectrometer (Bruker Avance (600/400) MHz)
Gel permeation chromatography (Waters 1525 system)
Thermogravimetric analysis (STA449F3 Jupiter)
Plant and instrument: with Nicolet IS10 determination of infrared spectroscopy infrared spectra; Nuclear magnetic resonance spectrum BrukerAvance (600/400) MHz nuclear magnetic resonance spectrometer measures, and analyzes, thus determine the chemical structural formula of this compound through carrying out detection to the product of embodiment 3.
The physico-chemical property of the compound prepared: outward appearance is white bar shaped crystal; Tasteless; Solvability: be slightly soluble in water, is dissolved in ethanol, sherwood oil, methylene dichloride and ethyl acetate organic solvent completely; Its molecular formula is C
26h
40o
4; Molecular weight is: 416.61.
Learnt by the infrared spectrogram of Fig. 1 dehydroabietic acid trihydroxymethylpropanyl ester, at the O-H stretching vibration peak that 3427.48cm-1 occurs, and occur the flexural vibration peak of O-H at 1037.37cm-1; Occur the stretching vibration peak of the C=O of ester at 1723.69cm-1,1246.86cm-1 has the stretching vibration peak of C-O, simultaneously in 900-950cm-1 without the flexural vibration peak of-OH in carboxylic acid, confirm there is no-COOH in this system.In addition, 2928.74cm-1 is the stretching vibration peak of-CH3; Symmetrical-CH2 stretching vibration occurs in the flexural vibration peak that 1464.05cm-1 and 1497.88cm-1 and 1384.73cm-1 are-CH3.Ester has all been changed into by the analytic explanation dehydroabietic acid of infrared spectra.
Fig. 2, the nucleus magnetic hydrogen spectrum figure of dehydroabietic acid trihydroxymethylpropanyl ester (DATE), belonged to known by structural analysis, 7.26ppm place is deuterochloroform solvent peak, three groups of peaks (two doublets of 6.89-7.17ppm, one is unimodal) fragmentation condition and DATE phenyl ring on the position residing for three hydrogen coincide, the appearance at 4.20ppm place is unimodal, coincide according to the hydrogen on the carbon (i.e. No. 26 carbon) that its displacement is connected with ester bond, hydrogen on the carbon that the quartet at 3.59ppm place is then connected with hydroxyl namely (24, No. 25 carbon) on H corresponding, again because 6.89-7.17ppm three groups of peaks with, the integration ratio of the quartet at the unimodal 3.59ppm place at 4.20ppm place is 1:1:1:2:4 just, corresponding with the numbers of hydrogen atoms on corresponding carbon, thus checking TriMethylolPropane(TMP) is combined with dehydroabietic acid further.Recording compound molecular weight by LC-MS is in addition 416,
1hNMR (399MHz, CDCl, ppm):, 7.17 (d, J=8.1Hz, 1H; Ar), 7.01 δ (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=9.3,5.9Hz, 3H) .MS (ESI, m/z) forC
26h
40o
4: 417 (M
+).
Fig. 3 is the nuclear-magnetism carbon spectrogram of dehydroabietic acid trihydroxymethylpropanyl ester (DATE), through measuring the signal of each carbon atom as described below: 13CNMR (100MHz, CDCl3, 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 figure of this compound, is 250 ~ 430 DEG C by analyzing its decomposition temperature that can obtain compound.
Determine that the name of this compound is called dehydroabietic acid trihydroxymethylpropanyl ester further by above analysis, chemical structural formula is as follows.
Further, respectively with compd A prepared by embodiment 3, identical detection is carried out to embodiment 1, embodiment 2, embodiment 4, embodiment 5 and enforcement 6 preparation-obtained compounds, infrared spectrogram, nucleus magnetic hydrogen spectrum figure, nuclear-magnetism carbon spectrogram and thermogravimetric analysis figure that all embodiments detect the result that obtains all corresponding with compd A are identical, and describe prepared product circulation ratio fabulous.
This Compound nomenclature is by applicant further: dehydroabietic acid trihydroxymethylpropanyl ester.
Further can confirm that the English name of this compound is trimethylolpropane dehydroabietyate.
Applicant confirms that the decomposition temperature of this compound is 250 ~ 430 DEG C further.
Three, further illustrate the purposes of dehydroabietic acid trihydroxymethylpropanyl ester with the following Examples, but protection domain is not limited only to following Application Example.
Application Example 1
Weigh the dehydroabietic acid trihydroxymethylpropanyl ester 0.01mol (4.2g) that embodiment 1 prepares, the Succinic anhydried of 0.01mol (1g), catalyzer tosic acid 0.2g, add successively in the three-necked flask of 150mL, install water trap reflux condensing tube additional and (connect moisture eliminator, safety flack, vacuum pump) thermometer of 300 DEG C, logical nitrogen stopped after 10 minutes, vacuumized, repeated 3 times.Logical nitrogen, starts heating, waits reactant to melt, and opens magneton and stirs, treat that temperature is elevated to 120 DEG C, keep this temperature, stops logical nitrogen, vacuumizes, and keep vacuum tightness to be greater than 0.09Mpa and start clock reaction 7 hours, reaction terminates.With dissolve with ethanol, being contained in molecular retention amount is in the dialysis tubing of 1000, dialyses 7 days respectively with second alcohol and water.Be spin-dried for, obtain dehydrogenation fir base succinic acid polyester.The dehydrogenation fir base succinic acid polyester prepared, has good rigidity and thermostability, can be applicable to tackiness agent and the hot melt coating of pressure-sensitive and heat-sensitive glue adhesive tape.
Gained dehydrogenation fir base succinic acid polyester is light yellow solid.Recorded by gel permeation chromatography, polymkeric substance number-average molecular weight is: 3400, and polymolecularity is 1.2.
Application Example 2
Weigh embodiment 3 prepare dehydroabietic acid trihydroxymethylpropanyl ester (DATE) 0.01mol (4.2g), the succinic acid (SA) of 0.01mol (1.18g), catalyzer tosic acid 0.2g, adds in the three-necked flask of 150mL successively, installs water trap reflux condensing tube additional and (connects moisture eliminator, safety flack, vacuum pump) thermometer of 300 DEG C, logical nitrogen 10 minutes, stops logical nitrogen, vacuumize, repeat 3 times.Logical nitrogen, starts heating, waits reactant to melt, and opens magneton and stirs, treat that temperature is elevated to 120 DEG C, keep this temperature, stops logical nitrogen, vacuumizes, and keep vacuum tightness to be greater than 0.09Mpa and start clock reaction 7 hours, reaction terminates.With dissolve with ethanol, being contained in molecular retention amount is in the dialysis tubing of 1000, dialyses 7 days respectively with second alcohol and water.Be spin-dried for, obtain dehydrogenation fir base succinic acid polyester.The dehydrogenation fir base succinic acid polyester prepared, has good rigidity and thermostability, can be applicable to tackiness agent and the hot melt coating of pressure-sensitive and heat-sensitive glue adhesive tape.
The preparation of dehydrogenation fir base succinic acid polyester (DSPE), its reaction equation is:
Gained dehydrogenation fir base succinic acid polyester is light yellow solid.Recorded by gel permeation chromatography, polymkeric substance number-average molecular weight is: 5215, and polymolecularity is 1.33.
Above-mentioned dehydrogenation fir base succinic acid polyester (DSPE) is carried out infrared detection, and the infrared spectrogram that detection obtains as shown in Figure 5.In Fig. 5, the infrared spectrogram of Dehydroabietic acid succinic acid polyester (DSPE), compared with the infrared spectrogram of accompanying drawing 1 dehydroabietic acid TriMethylolPropane(TMP), in DSPE figure, the hydroxyl peak of 3440 disappears, carbonyl peak also there occurs displacement relatively, infer that hydroxyl take part in esterification, and generate new ester.
Dehydrogenation fir base succinic acid polyester (DSPE) obtained above is carried out nucleus magnetic hydrogen spectrum detection, and the nucleus magnetic hydrogen spectrum figure that detection obtains as shown in Figure 6.Fig. 6 is in DSPE nuclear-magnetism figure, the result that mensuration obtains as described below, learn by analysis, hydrogen atom peak on contiguous hydroxyl C disappears, the hydrogen of contiguous ester group C increases simultaneously, newly connect the H also corresponding appearance of succinic acid, and integral result and theoretical H atom number coincide, and further demonstrate the generation of esterification.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)。
Fig. 7 is the thermogravimetric analysis of this polymkeric substance, and its decomposition temperature is 350 ~ 500 DEG C.
Confirm that the name of this compound is called dehydrogenation fir base succinic acid polyester further by analyzing above.
Application Example 3
Weigh the dehydroabietic acid trihydroxymethylpropanyl ester 0.01mol (4.2g) that embodiment 3 prepares, (0.42g) propanedioic acid, catalyzer tosic acid 0.2g, adds in the three-necked flask of 150mL successively, installs water trap reflux condensing tube additional and (connects moisture eliminator, safety flack, vacuum pump) thermometer of 300 DEG C, logical nitrogen 10 minutes, stops logical nitrogen, vacuumize, repeat 3 times.Logical nitrogen, starts heating, waits reactant to melt, and opens magneton and stirs, treat that temperature is elevated to 120 DEG C, keep this temperature, stops logical nitrogen, vacuumizes, and keep vacuum tightness to be greater than 0.09Mpa and start clock reaction 7 hours, reaction terminates.With dissolve with ethanol, being contained in molecular retention amount is in the dialysis tubing of 1000, dialyses 7 days respectively with second alcohol and water.Be spin-dried for, obtain dehydrogenation fir propylmalonic acid polyester.
Gained dehydrogenation fir propylmalonic acid polyester is white solid.Recorded by gel permeation chromatography, polymkeric substance number-average molecular weight is: 3892, and polymolecularity is 1.56, and by thermogravimetric analysis, its decomposition temperature is 320-480 DEG C.
The dehydrogenation fir propylmalonic acid polyester prepared, similar to dehydrogenation fir base succinate, there is good rigidity and thermostability, can be applicable to tackiness agent and the hot melt coating of pressure-sensitive and heat-sensitive glue adhesive tape.
Application Example 4
Weigh dehydrogenation fir base trihydroxymethylpropanyl ester 0.01mol (4.2g) and catalyzer KOH 0.003mol (0.168g) in embodiment 5 join autoclave and start to heat up, when temperature reaches 70 DEG C, with vacuum pump evacuation to gauge pressure at about-0.05MPa, N
2purge displacement, vacuumize 30 minutes, then temperature is 130 ± 5 DEG C time, and start interval and add oxyethane (EO), reactor pressure-controlling is at 0.2-0.4 MPa.After reinforced, when the pressure of reactor falls after rise, continue reaction at such a temperature until-0.05 MPa when being reduced to beginning, now react completely, obtained poly-dehydrogenation fir base ether.
Crude product and catalyzer KOH being dissolved in three water drips in a small amount of acetic acid, with membrane filtration removing impurity insolubles.By the dichloromethane institute extraction of the sample of gained, after being removed by extraction liquid rotary evaporation, at 65 DEG C, namely vacuum-drying obtain dehydrogenation fir polyethers for 24 hours.Rosin is nontoxic, can be used as medicine, be combined between polyethers with medicine with hydrogen bond action, can be used for pharmaceutical carrier, again because this material is amphipathic, can be used as tensio-active agent.
Application Example 5
Weigh the dehydroabietic acid ester 0.01mol (4.2g) that embodiment 1 prepares, the laurostearic acid (lauric acid) of 0.024mol (4.8g), catalyzer tosic acid 0.45g, add successively in the three-necked flask of 250mL, install water trap reflux condensing tube additional and (connect moisture eliminator, safety flack, vacuum pump) thermometer of 300 DEG C, logical nitrogen stopped after 10 minutes, vacuumized, repeated 3 times.Logical nitrogen, starts heating, waits reactant to melt, and opens magneton and stirs, treat that temperature is elevated to 120 DEG C, keep this temperature, stops logical nitrogen, vacuumizes, and keep vacuum tightness to be greater than 0.09Mpa and start clock reaction 7 hours, reaction terminates.With dissolve with ethanol, being contained in molecular retention amount is in the dialysis tubing of 500, dialyses 7 days respectively with second alcohol and water.Be spin-dried for, obtain the two laurate of dehydrogenation fir base.This product and common plasticizers octyl phthalate structural similitude, and the characteristic of its good cold performance and environment-protecting asepsis, the two laurate series product of dehydrogenation fir base are applied in PVC as environment-friendlyplasticizer plasticizer and properties-correcting agent has plastification, has good actual application value.
Claims (10)
1. rosin three alcohol ester, is characterized in that: the chemical name of described rosin three alcohol ester is: dehydroabietic acid trihydroxymethylpropanyl ester, and its chemical structural formula is:
This compound outward appearance is white bar shaped crystal; Tasteless; Solvability: be slightly soluble in water, is dissolved in ethanol, sherwood oil, methylene dichloride and ethyl acetate organic solvent completely; Decomposition temperature: 250-430 DEG C; Its molecular formula is C
26h
40o
4;molecular weight is: 416.61.
2. the preparation method of a kind of rosin three alcohol ester as claimed in claim 1, it is characterized in that: the preparation of this rosin three alcohol ester is for raw material with dehydroabietic acid and TriMethylolPropane(TMP), take EDC/DMAP as catalyzer, in organic solvent with under normal temperature esterification synthesis dehydroabietic acid trihydroxymethylpropanyl ester occurs, reaction formula is:
Dehydroabietic acid TriMethylolPropane(TMP) dehydroabietic acid trihydroxymethylpropanyl ester.
3. the preparation method of a kind of rosin three alcohol ester according to claim 2, is characterized in that: the mass ratio of above-described reaction mass is: dehydroabietic acid: TriMethylolPropane(TMP): DMAP:EDC=1.5:0.67 ~ 4.02:0.12 ~ 1:1.15 ~ 1.725.
4. the preparation method of a kind of rosin three alcohol ester according to claim 2, is characterized in that: described organic solvent is any one in methylene dichloride, tetrahydrofuran (THF) and DMF.
5. a kind of preparation method of rosin three alcohol ester as described in any one of claim 2-4, is characterized in that: the concrete steps of the method comprise:
1) add material to react: getting rid of in the reaction vessel of oxygen, add dehydroabietic acid and TriMethylolPropane(TMP) raw material, and add DMAP, they are dissolved in methylene dichloride or tetrahydrofuran (THF) or N, any one organic solvent of dinethylformamide, its consumption is: dehydroabietic acid: organic solvent=1g:12 ~ 20mL, after dissolving, cooling makes temperature be cooled to 0 DEG C, add EDC fast, starvation, after reaction 15 ~ 30min, recover normal temperature and continue reaction, stop after continuous stirring 10 ~ 24h, reaction terminates, above-mentioned reacted material is carried out revolving steaming, except desolventizing, obtain solid mixture,
Obtain crude product: by above-mentioned solid mixture dissolution with solvents, and use saturated common salt water washing, get organic layer, be spin-dried for, obtain dehydroabietic acid trihydroxymethylpropanyl ester crude product;
The purification of product: the compound that above-mentioned dehydroabietic acid trihydroxymethylpropanyl ester crude product can be obtained white bar shaped lenticular by column chromatography for separation, confirms as dehydroabietic acid trihydroxymethylpropanyl ester through structured testing.
6. the preparation method of a kind of rosin three alcohol ester according to claim 5, is characterized in that: described step 2) solvent is any one in sherwood oil, ethanol, methylene dichloride and ethyl acetate.
7. the preparation method of a kind of rosin three alcohol ester according to claim 6, is characterized in that: described in revolve steaming be with 50 ~ 200mL sherwood oil for solvent, be 40 ~ 50 DEG C and pressure in temperature be that 0.007 ~ 0.009MPa backspin steams 20 ~ 45min.
8. the preparation method of a kind of rosin three alcohol ester according to claim 5, it is characterized in that: described column chromatography is silica gel column chromatography, sorbent material used is silica gel, and eluent is petrol ether/ethyl acetate system, and consumption is 2/1 ~ 3/1 of pillar volume.
9. a kind of preparation method of rosin three alcohol ester according to any one of claim 5-8, is characterized in that: the dehydroabietic acid trihydroxymethylpropanyl ester that the method prepares, records high purity more than 95.5% by high performance liquid chromatography.
10. the application of rosin three alcohol ester according to claim 1, is characterized in that: rosin three alcohol ester can be applicable to pressure-sensitive and the tackiness agent of heat-sensitive glue adhesive tape, the softening agent of resin and properties-correcting agent, thermally melting coating, tensio-active agent and pharmaceutical carrier.
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| CN108854838A (en) * | 2018-06-20 | 2018-11-23 | 江南大学 | A kind of abietyl lactic acid surfactant and its application |
| CN110157372A (en) * | 2019-06-19 | 2019-08-23 | 南宝树脂（佛山）有限公司 | A kind of one-component PUD glue and preparation method thereof |
| CN110804159A (en) * | 2019-11-06 | 2020-02-18 | 桂林理工大学 | Rosin-based polyurethane resin for photocureable coating and preparation method thereof |
| CN113522159A (en) * | 2021-07-19 | 2021-10-22 | 深圳建实科技有限公司 | Surfactant with triple structure and preparation method thereof |
| CN113522159B (en) * | 2021-07-19 | 2022-07-26 | 深圳建实科技有限公司 | Surfactant with triple structure and preparation method thereof |
| CN113816849A (en) * | 2021-10-11 | 2021-12-21 | 上海安谱实验科技股份有限公司 | Synthesis method of di (4-methyl-2-pentyl) phthalate or stable isotope label thereof |
| CN115181258A (en) * | 2022-06-13 | 2022-10-14 | 福州大学 | Rosin-terminated polyether block copolymer surfactant and preparation method thereof |
| CN115181258B (en) * | 2022-06-13 | 2023-10-13 | 福州大学 | Rosin-terminated polyether block copolymer surfactant and preparation method thereof |
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