CN103952082A - Method for preparing abietinol - Google Patents
Method for preparing abietinol Download PDFInfo
- Publication number
- CN103952082A CN103952082A CN201410164274.4A CN201410164274A CN103952082A CN 103952082 A CN103952082 A CN 103952082A CN 201410164274 A CN201410164274 A CN 201410164274A CN 103952082 A CN103952082 A CN 103952082A
- Authority
- CN
- China
- Prior art keywords
- rosin
- reaction
- pressure
- still
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing abietinol. The method comprises the following steps: dissolving a rosin ester into normal hexane, sequentially adding the mixture and a Cu-Zn catalyst to a high-pressure reactor; introducing hydrogen, carrying out heating and pressurizing reaction; introducing condensate water to quickly cool to room temperature after reaction is ended; releasing pressure and discharging; recovering the normal hexane, wherein the obtained light yellow viscous liquid is a crude abietinol product; carrying out vacuum distillation on the crude abietinol product at the pressure being below 26.58Pa, so as to obtain transparent viscous liquid, namely abietinol. According to the preparation method of the abietinol disclosed by the invention, the yield of abietinol transformed from methyl abietate is 82.1%, the yield of abietinol transformed from rosin acid n-butyl ester is 72.1%, and the yield of abietinol transformed from rosin acid octyl ester is 64.9% under the technology conditions that the temperature is 270 DEG C, the mass ratio of the rosin ester to the normal hexane is 1:3, the reaction pressure is 10MPa, and the reaction time is 11 hours; the abietinol product with high yield is obtained; a technology which is low in cost, low in requirements on equipment and safe to operate is provided for industrial production of abietinol.
Description
Technical field
The invention belongs to rosin derivative preparing technical field, be specifically related to a kind of preparation method of rosin alcohol.
Background technology
Rosin is a kind of reproducible natural resin, be described as " lignicolous oil ", tap oozy thick liquid rosin from pinaceae plant or its congener trunk, melt, melt the clean system of fat liquid and fat liquid distillation processed and a kind of hard fragility the transparent unformed natural resin that obtain only through rosin.Rosin is yellow to brown solid, is soluble in alcohol, acetone, acetic acid, turpentine wet goods, and the solvability in gasoline, kerosene is poor, is insoluble to cold water, and in hot water, part is emulsified.The rosin of different sources has similar composition, but its chemical structure complexity, resinous acid and a small amount of fatty acid content are more than 90%, and all the other less thaies 10% are neutral substance and ash content.That rosin has is anticorrosion, insulation, the good characteristic such as bonding and be widely used, but can find out the chemical structure of rosin, in resinous acid, contain unsaturated link(age), make it have that oxidation-resistance is poor, the easy shortcoming such as crisp, easy crystallization, poor heat stability, apply more widely at many industrial sectors thereby limited to it.In order to overcome its shortcoming, conventionally rosin is carried out modification or is prepared into derivative.In abietic type acid, there are two chain carriers---carboxyl and conjugated double bond, therefore can carry out chemical modification or derivative for these two active sites, thereby give the character of rosin to expect.
Rosin alcohol outward appearance is colourless viscous liquid, is a kind of important derivatives product of rosin, is a kind of important surrogates in some high-end applications fields.It is low that rosin alcohol has acid number, and thermostability is high, and acidproof, alkaline-resisting ability is strong, and because saturation ratio is high, have better antioxidant property than other rosin derivative.Rosin alcohol of many uses, comprise the additive making chewing gum base, make preventing light agent, make colourless environmental protection cleaning-free scaling powder, improvement synthetic wax (wax of manufacturing with hydrogenated castor oil especially), as external plasticizer or the internal plasticizer of for example branched polyamides, polymerized rosin, Precondensed UreaFormaldehyde Resin and resol of plastics, and share with mineral oil, for production of microelectronic circuit plate etc.In addition, rosin alcohol is also important chemical intermediate, can be used for making a series of important ether compounds.The preparation of rosin alcohol is the process that the carboxyl hydrogenolysis reducing in rosin acid is become to hydroxyl.Because carboxyl in rosin acid is positioned on tertiary carbon atom, be subject to the impact of the luxuriant and rich with fragrance skeleton of ternary, sterically hindered large, reaction activity is high.Meanwhile, resinate hydrogenolysis reducing belongs to gas-liquid-solid three-phase process, and the solubleness in is mutually extremely low at resinate for hydrogen, causes catalyst surface to lack hydrogen, therefore synthetic severe reaction conditions.Traditional rosin alcohol production technique is that chromic salt is catalyzer, under the condition of about 20MPa, 300 DEG C of atmosphere of hydrogen, carries out hydrogenolysis reducing reaction taking rosin or rosin ester as raw material.Its working condition is high to equipment requirements, and in chromate catalyst preparation process, has a large amount of hexavalent chromiums to flow into mother liquor, causes serious environmental pollution.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of rosin alcohol, make it have low cost, the feature such as lower and operational safety to equipment requirements.
Technical scheme: for achieving the above object, the present invention adopts following technical scheme:
The preparation method of rosin alcohol: rosin ester is dissolved in to a normal hexane, successively adds in the autoclave that whipping appts is housed sealing kettle cover with the Cu-Zn catalyzer of processing through reduction; In still, pass into nitrogen replacement air, after repetitive operation three times, start heated and stirred; Be warming up to temperature of reaction, pass into hydrogen, regulate still internal pressure to setting reaction pressure, start reaction; After reaction finishes, logical water of condensation is down to room temperature, pressure release, discharging fast; Reclaim normal hexane, gained light yellow viscous liquid is rosin alcohol crude product; Rosin alcohol crude product carries out underpressure distillation and obtains transparent thick liquid under < 26.58Pa pressure, is rosin alcohol.
Wherein, the mass ratio of rosin ester and normal hexane is 1:1～4, and reaction pressure is 8～10MPa, and the reaction times is 8～14h, and temperature of reaction is 250～280 DEG C; Cu-Zn catalyst levels is 10% of rosin ester quality.
Described temperature of reaction is 270 DEG C, and the mass ratio of rosin ester and normal hexane is 1 ︰ 3, and reaction pressure is 10MPa, and the reaction times is 11h.
Described rosin ester is selected from rosin manthanoate, the positive butyl ester of sylvic acid and sylvic acid n-octyl.
Described methyl abietate is prepared by following methods: 20g is shattered to rosin, 0.2g solid acid catalyst ZnO and methyl alcohol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, passing into nitrogen regulates still internal pressure to carry out esterification to 5.5MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of methyl alcohol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid methyl abietate crude product; Methyl abietate crude product carries out underpressure distillation and obtains brown color thick liquid methyl abietate under < 26.58Pa pressure, and wherein, the mol ratio of methyl alcohol and rosin is 25 ︰ 1.
The positive butyl ester of described sylvic acid is prepared by following methods: 20g is shattered to rosin, 0.2g solid acid catalyst ZnO and propyl carbinol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, passing into nitrogen regulates still internal pressure to carry out esterification to 3.5MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of propyl carbinol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out the positive butyl ester crude product of reddish-brown thick liquid sylvic acid; The positive butyl ester crude product of sylvic acid carries out underpressure distillation and obtains the positive butyl ester of brown color thick liquid sylvic acid under < 26.58Pa pressure, and wherein, the mol ratio of propyl carbinol and rosin is 25 ︰ 1.
Described sylvic acid n-octyl is prepared by following methods: 20g is shattered to rosin, 0.2g solid acid catalyst ZnO and n-Octanol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 210 DEG C, passing into nitrogen regulates still internal pressure to react to 2.0MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of n-Octanol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid sylvic acid n-octyl crude product; The positive fourth monooctyl ester of sylvic acid crude product carries out underpressure distillation and obtains brown color thick liquid rosin n-octyl under < 26.58Pa pressure; Wherein, the mol ratio of n-Octanol and rosin is 8 ︰ 1.
Beneficial effect: compared with prior art, the preparation method of rosin alcohol of the present invention, at technology condition be: 270 DEG C of temperature, rosin ester and normal hexane mass ratio are 1 ︰ 3, reaction pressure 10MPa, under the condition of reaction times 11h, the yield that following rosin ester is converted into rosin alcohol is: methyl abietate 82.1%, the positive butyl ester 72.1% of sylvic acid, sylvic acid n-octyl 64.9%, all obtain the rosin alcohol product of higher yield, for the suitability for industrialized production of rosin alcohol provides the Technology of a low cost, and operational safety lower to equipment requirements.
Brief description of the drawings
Fig. 1 is methyl abietate mass spectrum;
Fig. 2 is the main faults mode figure of methyl abietate;
Fig. 3 is the positive butyl ester mass spectrum of abietic acid;
Fig. 4 is abietic acid n-octyl mass spectrum;
Fig. 5 is the GC-MS total ion current figure of three kinds of rosin esters;
Fig. 6 is the infrared spectrogram of rosin and three kinds of rosin esters;
Fig. 7 is the GC-MS total ion current figure of rosin alcohol and each rosin ester hydrogenolysis reducing product;
Fig. 8 is the infrared spectrogram of each rosin ester and hydroformylation product solution thereof.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
The main raw material, reagent and the instrument that in following examples, use are as follows:
Raw material and reagent: rosin (industry is superfine, acid number: 169mgkOH/g); Methyl alcohol, propyl carbinol, n-Octanol, zinc oxide, ethyl acetate etc., be AR level, purchased from Nanjing Chemistry Reagent Co., Ltd. and Chemical Reagent Co., Ltd., Sinopharm Group.Rosin alcohol sample (Jin Tenglong trade Co., Ltd of Shenzhen, imported from America); Cu-Zn catalyzer (Nanjing Zun Long Chemical Co., Ltd.); Normal hexane (critical temperature T
c: 507K; Emergent pressure P
c: 2.97MPa).
Instrument: WHF-0.25 type autoclave (automatic control reactor company limited of Weihai in Shandong province); NICOLET380 type Fourier transformation infrared spectrometer (power & light company of the U.S.); 5975/7890 gas-matter combination analysis instrument (Agilent company of the U.S.).OTL1200 tube furnace (Nanjing Nanda Instrument Plant); Combined multifunctional horizontal X-x ray diffractometer x (Amada Co., Ltd.'s Neo-Confucianism); 7890A gas chromatograph (Agilent company of the U.S.).
The analytical procedure and the condition that in following examples, use are as follows:
Determination of acid value: the method for measuring staybelite acid number by GB GB/T14020-92 is surveyed its acid number, and the esterification yield of rosin is calculated as follows: esterification yield=(1-product acid number/raw material acid number) × 100%.
Rosin ester hydrogenolysis reducing product carries out qualitative analysis by gas chromatograph-mass spectrometer (GC-MS), and gas chromatograph carries out quantitative analysis (external standard method).Rosin ester transformation efficiency calculation formula is: rosin ester transformation efficiency=(M
1-M
2)/M
1× 100%.
In formula, M
1for raw material rosin ester quality; M
2for rosin ester quality in product.
Rosin alcohol selective calculation formula is: rosin alcohol selectivity=M/ (M
1-M
2) × 100%.In formula, M is the required rosin ester quality of the amount theory of computation of rosin alcohol in product; M
1for raw material rosin ester quality; M
2for rosin ester quality in product.
FT-IR analyzes: adopt respectively pellet technique (solid sample) and liquid film method (liquid sample) sample preparation, scan 32 times, data are analyzed with OriginPro8 process software.
GC/MS analyzes: GC analysis condition: and use HP-5MS (m) nonpolar chromatographic column of μ m × 0.25,30m × 250 μ, high-purity helium is carrier gas, and vaporizer temperature is 300 DEG C, and sensing chamber's temperature is 250 DEG C; Heating schedule: 100 DEG C of starting temperatures are for 2 minutes, by 10 DEG C/min to 220 DEG C, by 5 DEG C/min to 260 DEG C, then by 10 DEG C/min to 280 DEG C, for 10 minutes; Before post, press: 10.523psi; Splitting ratio: 50: 1; Sample size: 0.2uL.
MS analysis condition: electron bombardment ionization source (EI); Electron energy 70eV; 250 DEG C of interface temperatures; Multiplier electrode 1.2kV; Mass scanning scope 50-400u; Scanning interval 0.5s.
XRD analysis, analysis condition: Cu/Ka target, operating voltage 40kV, working current 100mA, step-scan, 2 θ are 10 °-80 °, 8 °/min of scanning speed.
The standard map that NIST database in gained mass spectrum and this machine detects contrasts, and carries out qualitative analysis.
Embodiment 1
Adopt ZnO to make catalyzer, under stress rosin catalyzed and monohydroxy-alcohol esterification is prepared sylvic acid esterification product.Specific as follows:
1) preparation of methyl esters of rosin
20g is shattered to rosin, solid acid catalyst ZnO, and taking rosin consumption as 1%, (massfraction, lower with) and methyl alcohol add in the autoclave that whipping appts is housed, and seal kettle cover.In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, passing into nitrogen regulates still internal pressure to react to 5.5MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of methyl alcohol unnecessary in still and generation is reclaimed, until pressure makes zero.When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid rosin ester crude product.Wherein, the mol ratio of methyl alcohol and rosin is 25 ︰ 1.
Methyl abietate crude product carries out underpressure distillation and obtains brown color thick liquid methyl abietate under < 26.58Pa pressure.The acid number that records methyl abietate is 14.9, and esterification yield is 91.2.
The GC-MS analytical results of methyl abietate and Main Components mass spectrum are in table 1 and Fig. 1.
The GC-MS of table 1 methyl abietate product analyzes
Methyl abietate product is made up of the isomers of structural similitude, taking methyl abietate as example, in conjunction with its fragmentation pattern that ionization occurs through mass spectrometer of its mass spectrogram analysis.Mass spectrum 1 from methyl abietate is analyzed, and molion mass-to-charge ratio is 316, shows that corresponding compound molecule mass M is 316, conforms to the molecular weight of methyl abietate, and its mass-spectrometric data is as shown in table 1.The molion peak intensity of this compound is larger, illustrates that this compound molecule ionic structure stability is better, and this and methyl abietate are that the character of cyclisation thing matches.Mass-to-charge ratio is that 257 fragment ion peak can think that molecule loses one through alpha cleavage
+o ≡ C-OCH
3after fragment, obtain, this fragment ion peak abundance is 100, is base peak, represents that this fragmention is very stable, and this also meets the feature of cyclisation thing fragmention.The possible main fragmentation pattern of methyl abietate as shown in Figure 2.
2) preparation of the positive butyl ester of sylvic acid
20g is shattered to rosin, solid acid catalyst ZnO, and taking rosin consumption as 1%, (massfraction, lower with) and propyl carbinol add in the autoclave that whipping appts is housed, and seal kettle cover.In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, passing into nitrogen regulates still internal pressure to react to 3.5MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of alcohol unnecessary in still and generation is reclaimed, until pressure makes zero.When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out the positive butyl ester crude product of reddish-brown thick liquid sylvic acid.Wherein, the mol ratio of propyl carbinol and rosin is 25 ︰ 1.
The positive butyl ester crude product of sylvic acid carries out underpressure distillation and obtains the positive butyl ester of brown color thick liquid sylvic acid under < 26.58Pa pressure.The acid number that records the positive butyl ester of sylvic acid is 12.6, and esterification yield is 92.5.
The GC-MS analytical results of the positive butyl ester of sylvic acid and Main Components mass spectrum are in table 2 and Fig. 3.Methyl abietate, positive butyl ester and n-octyl product structure are similar, and its fragmentation pattern ruptures referring to methyl abietate, below do not repeat.
The GC-MS of the positive fourth esterification products of table 2 sylvic acid analyzes
3) preparation of sylvic acid n-octyl
20g is shattered to rosin, solid acid catalyst ZnO, and taking rosin consumption as 1%, (massfraction, lower with) and n-Octanol add in the autoclave that whipping appts is housed, and seal kettle cover.In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 210 DEG C, passing into nitrogen regulates still internal pressure to react to 2.0MPa, reaction 5h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of alcohol unnecessary in still and generation is reclaimed, until pressure makes zero.When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid sylvic acid n-octyl crude product.Wherein, the mol ratio of n-Octanol and rosin is 8 ︰ 1.
The positive fourth monooctyl ester of sylvic acid crude product carries out underpressure distillation and obtains brown color thick liquid sylvic acid n-octyl under < 26.58Pa pressure.Recording its acid number is 7.1, and esterification yield is 95.8.
The GC-MS analytical results of sylvic acid n-octyl and Main Components mass spectrum are in table 3 and Fig. 4.
The GC-MS of table 3 rosin n-octyl product analyzes
Adopt GC/MS analyser to analyze sylvic acid esterification product, its total ions chromatogram is shown in Fig. 5, and in figure, a is methyl abietate, and b is the positive butyl ester of sylvic acid, and c is sylvic acid n-octyl.From the total ions chromatogram of rosin ester, esterification products is 4-5 component, utilize mass-spectrometric data storehouse retrieval connexus spectrum analysis automatically, the primary product of having determined esterification is abietate, this and abietic type acid are heated isomerization reaction easily occur, and the most stable character of isomery proneness of abietic acid matches.
2) sylvic acid esterification product FT-IR analyzes
Raw material rosin and the spectroscopic analysis of rosin ester infrared spectroscopy, analytical results is shown in Fig. 6 and table 4, and in Fig. 6, a is rosin, and b is methyl abietate, and c is the positive butyl ester of sylvic acid, d is sylvic acid n-octyl.
The Infrared spectroscopy of table 4 rosin and rosin ester
Can find out by contrast: the vibration peak that product rosin ester occurs at 2930cm-1,1460cm-1,1385cm-1 place is the vibration performance of methyl, methylene radical, these peaks obviously strengthen compared with raw material rosin spectrogram, this is because introduce methyl (methyl esters is that 1, positive butyl ester are that 3, n-octyl are 4) and methylene radical after synthetic rosin ester on raw material rosin carboxyl, and the coupled vibration peak of methyl, methylene radical is strengthened; The C=O stretching vibration that is ester group at the strong absorption peak at 1725cm-1 place, the C-O stretching vibration that the strong absorption peak at 1242cm-1 and 1170cm-1 place is ester group, has loseed the carboxyl characteristic peak of raw material rosin at 3413.8cm-1 and 1696.5cm-1 place; In sylvic acid n-octyl infrared spectrum, the vibration peak occurring at 720cm-1 place is carbochain-(CH2) n-, the rocking vibration feature of n>4.
Embodiment 2
Raw material: methyl abietate, the positive butyl ester of sylvic acid, sylvic acid n-octyl, all can be commercially available product, and the present embodiment adopts embodiment 1 to prepare.
GC analyzes, GC analysis condition: and use HP-WAXETR (m) polarity chromatographic column of 30m x250 μ m x0.25 μ, high-purity helium is carrier gas, and vaporizer temperature is 260 DEG C, and sensing chamber's temperature is 250 DEG C; Heating schedule: 100 DEG C of starting temperatures, for 2 minutes, by 10 DEG C/min to 230 DEG C, by 3 DEG C/min to 260 DEG C, keep 10min; Before post, press: 10.523psi; Splitting ratio: 50: 1; Sample size: 2uL.
GC/MS analyzes, GC analysis condition: and use HP-5MS (m) nonpolar chromatographic column of 30m x250 μ m x0.25 μ, high-purity helium is carrier gas, and vaporizer temperature is 300 DEG C, and sensing chamber's temperature is 250 DEG C; Heating schedule: 100 DEG C of starting temperatures are for 2min, by 10 DEG C/min to 220 DEG C, by 2 DEG C/min to 270 DEG C, then by 10 DEG C/min to 300 DEG C, for 10min; Before post, press: 10.523psi; Splitting ratio: 50: 1; Sample size: 0.2uL.
The reduction of Cu-Zn catalyzer is carried out in tube furnace.Appropriate unreduced Cu-Zn catalyzer is put into ceramic disc and be placed in pipe furnace thorax middle part, boiler tube two ends are heat insulation stove plug beyond the Great Wall, loads onto steam stove flange.Connect hydrogen gas circuit, leak detection, displacement stove air in tube.Heat up by following heating schedule: room temperature 2h is warming up to 80 DEG C, and 10h is warming up to 150 DEG C, and 8h is warming up to 190 DEG C, and 3h is warming up to 240 DEG C, insulation 2h.The Cu-Zn catalyzer of reduction is positioned in methyl alcohol freezing, prevent its oxidation, for hydrogenolysis for subsequent use.
Working method is: rosin ester is dissolved in to normal hexane, successively adds in the autoclave that whipping appts is housed sealing kettle cover with the Cu-Zn catalyzer (taking rosin ester consumption as 10%, massfraction) of processing through reduction.In still, pass into nitrogen replacement air, after repetitive operation three times, start heated and stirred.Be warming up to temperature of reaction, pass into hydrogen, regulate still internal pressure to setting reaction pressure, start reaction.After reaction finishes, logical water of condensation is down to room temperature, pressure release, discharging fast.Reclaim normal hexane, gained light yellow viscous liquid is rosin alcohol crude product.
Rosin alcohol crude product carries out underpressure distillation and obtains transparent thick liquid and be rosin alcohol under < 26.58Pa pressure.
1) method is the same, wherein, rosin ester 15g, normal hexane 45g, reaction pressure is 10MPa, reaction 11h, result is as table 4.
The impact of table 4 temperature of reaction on rosin ester hydrogenolysis reducing reaction result
Note: in table, data are, transformation efficiency/selectivity, (unit: %, lower same).
As shown in Table 4, temperature of reaction is larger on the hydrogenolysis reducing reaction result impact of rosin ester.Along with the rising of temperature, the transformation efficiency of rosin ester increases gradually, and selectivity is downward trend.Consider transformation efficiency and selectivity, determine that 270 DEG C for optimal reaction temperature.
2) method is the same, wherein, rosin ester 15g, normal hexane consumption is as shown in table 5, and reaction pressure is 10MPa, reaction 11h, 270 DEG C of temperature of reaction, result is as table 5.
The impact of table 5 normal hexane consumption on rosin ester hydrogenolysis reducing reaction result
As shown in Table 5, in rosin ester hydrogenolysis reducing process, the interpolation of supercutical fluid normal hexane makes more than the transformation efficiency of methyl abietate can improve twice.In addition, the mass ratio of rosin ester and normal hexane is during by 1 ︰ 1 to 1 ︰ 3, and transformation efficiency and the selectivity of rosin ester increase gradually, continue to increase the ratio of normal hexane, and the transformation efficiency of rosin ester starts to decline.Therefore, rosin ester and normal hexane are advisable by 1 ︰ 3 proportionings in mass ratio.
3) method is the same, wherein, rosin ester 15g, normal hexane 45g, reaction pressure is as shown in table 6, reaction 11h, 270 DEG C of temperature of reaction, result is as table 6.
The impact of table 6 reaction pressure on rosin ester hydrogenolysis reducing reaction result
As shown in Table 6, along with the increase of reaction pressure, transformation efficiency and the selectivity of rosin ester are in rising trend.Can find out from experimental data trend, reaction pressure continues to strengthen, and the yield of rosin alcohol also can increase, but considers cost control, equipment requirements and processing safety in course of industrialization, and selecting optimum response pressure is 10MPa.
4) method is the same, wherein, rosin ester 15g, normal hexane 45g, reaction pressure 10MPa, 270 DEG C of temperature of reaction, the reaction times, result was as table 7 as table 7.
The impact of table 7 reaction times on rosin ester hydrogenolysis reducing reaction result
As shown in Table 7, within certain reaction times, along with the prolongation in reaction times, transformation efficiency and the selectivity of rosin ester increase gradually, exceed after 11h, and selectivity is obvious downtrending.Consider, determine that the suitable reaction times is 11h.
Each rosin ester hydrogenolysis reducing product and sample rosin alcohol are carried out to GC-MS analysis, gained total ions chromatogram is shown in Fig. 7, and in figure, a is sample rosin alcohol, and b is methyl abietate hydroformylation product solution, c is the positive butyl ester hydroformylation product solution of sylvic acid, and d is sylvic acid n-octyl hydroformylation product solution.From the total ions chromatogram of each product, reduzate has 3-4 component, and this and raw material rosin ester are for to be formed and to be matched by 3-4 kind resinate.Utilize mass-spectrometric data storehouse retrieval connexus spectrum analysis automatically, the main component of having determined product is dihydro pimarinol, dihydroabietyl alcohol, tetrahydroabietyl alcohol, dehydroabietinol etc., matches with sample rosin alcohol composition, and its each composition mass spectrometry results is in table 8.
The GC-MS analytical results of table 8 rosin ester hydrogenolysis reducing product
Respectively each rosin ester raw material and hydrogenolysis reducing product thereof are done to infrared spectroscopy spectroscopic analysis, analytical results is shown in Fig. 8 and table 9, and in Fig. 8, a1 is methyl abietate, a
2for methyl abietate hydroformylation product solution, b
1for the positive butyl ester of sylvic acid, b
2for the positive butyl ester hydroformylation product solution of sylvic acid, c
1for sylvic acid n-octyl, c
2for sylvic acid n-octyl hydroformylation product solution.
The Infrared spectroscopy of table 9 rosin and rosin ester
From Fig. 8, contrast and can find out: in each rosin ester product infrared spectrum, at 2885cm
-1, 1460cm
-1, 1385cm
-1the absorption peak at place is the eigen vibration of methyl, methylene radical, obviously weakens compared with rosin ester raw material spectrogram, visible raw material rosin ester by hydrogenolysis reducing after ,-OR (R=1,4,8) leaves away, and the coupled vibration peak of methyl, methylene radical is weakened; At 3400cm
-1, 1050cm
-1the hydroxyl that the strong absorption peak at place is primary alconol and the stretching vibration feature of C-O, be in a ratio of newly-increased peak with raw material; At 1770cm
-1, 1725cm
-1and 1690cm
-1ester group C=O and the C-O stretching vibration at place obviously weaken even and disappear compared with raw material, and the ester group of visible raw material rosin ester is hydroxyl by hydrogenolysis reducing.
Claims (6)
1. a preparation method for rosin alcohol, is characterized in that: rosin ester is dissolved in to normal hexane, successively adds in the autoclave that whipping appts is housed sealing kettle cover with the Cu-Zn catalyzer of processing through reduction; In still, pass into nitrogen replacement air, after repetitive operation three times, start heated and stirred; Be warming up to temperature of reaction, pass into hydrogen, regulate pressure to setting reaction pressure, start reaction; After reaction finishes, logical water of condensation is down to room temperature, pressure release, discharging fast; Reclaim normal hexane, gained light yellow viscous liquid is rosin alcohol crude product; Rosin alcohol crude product carries out underpressure distillation and obtains transparent thick liquid and be rosin alcohol under < 26.58Pa pressure;
Wherein, the mass ratio of rosin ester and normal hexane is 1:1 ~ 4, and reaction pressure is 8 ~ 10MPa, and the reaction times is 8 ~ 14h, and temperature of reaction is 250 ~ 280 DEG C; Cu-Zn catalyst levels is 10 % of rosin ester quality.
2. the preparation method of rosin alcohol according to claim 1, is characterized in that: described temperature of reaction is 270 DEG C, and the mass ratio of rosin ester and normal hexane is 1 ︰ 3, and reaction pressure is 10MPa, and the reaction times is 11h.
3. the preparation method of rosin alcohol according to claim 1, is characterized in that: described rosin ester is selected from methyl abietate, the positive butyl ester of sylvic acid and sylvic acid n-octyl.
4. the preparation method of rosin alcohol according to claim 3, is characterized in that: described methyl abietate is prepared by following methods:
20 g are shattered to rosin, 0.2 g solid acid catalyst ZnO and methyl alcohol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, passing into nitrogen regulates still internal pressure to carry out esterification to 5.5MPa, react 5 h, after finishing, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of alcohol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid methyl abietate crude product; Methyl abietate crude product carries out underpressure distillation and obtains transparent thick liquid methyl abietate under < 26.58Pa pressure;
Wherein, the mol ratio of methyl alcohol and rosin is 25 ︰ 1.
5. the preparation method of rosin alcohol according to claim 3, is characterized in that: the positive butyl ester of described sylvic acid is prepared by following methods:
20 g are shattered to rosin, 0.2 g solid acid catalyst ZnO and propyl carbinol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 220 DEG C, pass into nitrogen and regulate still internal pressure to 3.5 MPa to carry out esterification, after reacting 5 h, finish, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of alcohol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out the positive butyl ester crude product of reddish-brown thick liquid sylvic acid; The positive butyl ester crude product of sylvic acid carries out underpressure distillation and obtains the positive butyl ester of brown color thick liquid sylvic acid under < 26.58Pa pressure, and wherein, the mol ratio of propyl carbinol and rosin is 25 ︰ 1.
6. the preparation method of rosin alcohol according to claim 3, is characterized in that: described sylvic acid n-octyl is prepared by following methods:
20 g are shattered to rosin, 0.2 g solid acid catalyst ZnO and n-Octanol and add in the autoclave that whipping appts is housed, sealing kettle cover; In still, pass into nitrogen three times, displace after air, start heated and stirred, be warming up to 210 DEG C, pass into nitrogen and regulate still internal pressure to 2.0 MPa to carry out esterification, after reacting 5 h, finish, when keeping temperature of reaction, utilize still internal pressure, open and connect kettle upper discharge hole valve, the water of alcohol unnecessary in still and generation is reclaimed, until pressure makes zero; When reaction mass is cooled to below 50 DEG C in still, open reaction kettle cover, take out reddish-brown thick liquid sylvic acid n-octyl crude product; Sylvic acid n-octyl crude product carries out underpressure distillation and obtains brown color thick liquid sylvic acid n-octyl under < 26.58Pa pressure, and wherein, the mol ratio of n-Octanol and rosin is 8 ︰ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410164274.4A CN103952082B (en) | 2014-04-22 | 2014-04-22 | Method for preparing abietinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410164274.4A CN103952082B (en) | 2014-04-22 | 2014-04-22 | Method for preparing abietinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103952082A true CN103952082A (en) | 2014-07-30 |
| CN103952082B CN103952082B (en) | 2015-04-01 |
Family
ID=51329447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410164274.4A Expired - Fee Related CN103952082B (en) | 2014-04-22 | 2014-04-22 | Method for preparing abietinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103952082B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610053A (en) * | 2015-01-23 | 2015-05-13 | 中国林业科学研究院林产化学工业研究所 | Rosin derivate for soldering flux and preparation method |
| CN105860854A (en) * | 2016-05-13 | 2016-08-17 | 广西融水闽兴树脂有限公司 | Water-white rosin production line |
| CN106045812A (en) * | 2016-06-26 | 2016-10-26 | 广西众昌树脂有限公司 | Production method of abietinol |
| CN106065291A (en) * | 2016-06-26 | 2016-11-02 | 广西众昌树脂有限公司 | The preparation method of abienol |
| CN106118486A (en) * | 2016-06-26 | 2016-11-16 | 广西众昌树脂有限公司 | The production method of Sucrose Ester of Rosin Acid |
| CN108503732A (en) * | 2018-04-28 | 2018-09-07 | 中国林业科学研究院林产化学工业研究所 | Dehydrogenation fir base amide internal plasticization PVC material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003321651A (en) * | 2002-04-27 | 2003-11-14 | Rika Fainteku:Kk | Hydrogenated rosin and production thereof |
| CN102531840A (en) * | 2012-01-16 | 2012-07-04 | 中国林业科学研究院林产化学工业研究所 | Saturated rosin tribasic alcohol as well as preparation method and application thereof |
-
2014
- 2014-04-22 CN CN201410164274.4A patent/CN103952082B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003321651A (en) * | 2002-04-27 | 2003-11-14 | Rika Fainteku:Kk | Hydrogenated rosin and production thereof |
| CN102531840A (en) * | 2012-01-16 | 2012-07-04 | 中国林业科学研究院林产化学工业研究所 | Saturated rosin tribasic alcohol as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 尹斌等: ""加压条件下制备系列松香一元醇酯"", 《福建林业科技》, vol. 41, no. 1, 31 March 2014 (2014-03-31), pages 14 - 18 * |
| 张峻炜等: ""脂肪酸酯催化加氢制脂肪醇研究进展"", 《广州化工》, vol. 41, no. 3, 28 February 2013 (2013-02-28), pages 32 - 33 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610053A (en) * | 2015-01-23 | 2015-05-13 | 中国林业科学研究院林产化学工业研究所 | Rosin derivate for soldering flux and preparation method |
| CN105860854A (en) * | 2016-05-13 | 2016-08-17 | 广西融水闽兴树脂有限公司 | Water-white rosin production line |
| CN106045812A (en) * | 2016-06-26 | 2016-10-26 | 广西众昌树脂有限公司 | Production method of abietinol |
| CN106065291A (en) * | 2016-06-26 | 2016-11-02 | 广西众昌树脂有限公司 | The preparation method of abienol |
| CN106118486A (en) * | 2016-06-26 | 2016-11-16 | 广西众昌树脂有限公司 | The production method of Sucrose Ester of Rosin Acid |
| CN108503732A (en) * | 2018-04-28 | 2018-09-07 | 中国林业科学研究院林产化学工业研究所 | Dehydrogenation fir base amide internal plasticization PVC material and preparation method thereof |
| CN108503732B (en) * | 2018-04-28 | 2020-06-30 | 中国林业科学研究院林产化学工业研究所 | Dehydroabietyl amide internal plasticization PVC material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103952082B (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103952082B (en) | Method for preparing abietinol | |
| CN106008193B (en) | Method for catalytically oxidizing lignite by using oxygen as oxidant under normal pressure | |
| CN102584582B (en) | Preparing technology of hydroxyethyl acrylate | |
| CN111039769B (en) | Method for synthesizing methyl heptenone from methyl butynol | |
| CN106349014B (en) | Method for preparing 1, 4-pentanediol by utilizing levulinic acid ester | |
| CN104422748A (en) | Method for evaluating hydrogen donating ability of hydrogen donor for reaction matrix | |
| CN108358749B (en) | Method for producing propargyl alcohol | |
| CN105646227B (en) | A kind of method that levulinate is prepared using furfuryl alcohol | |
| CN114177930A (en) | Method for catalyzing lignin hydrogenation depolymerization by molecular sieve supported ruthenium-nickel catalyst | |
| CN106883765B (en) | Preparation method of hydrogenated rosin pentaerythritol ester | |
| CN111215138B (en) | Catalyst, preparation method and application of catalyst in preparation of beta-isophorone | |
| CN105693486B (en) | The method that 2,5 acetyl butyryls and 3 methyl cyclopentene ketone are prepared using 5 hydroxymethylfurfurals | |
| CN114644605B (en) | Method for preparing 2-methyltetrahydrofuran from waste biomass | |
| CN106946922B (en) | A kind of synthetic method of tri- boron compound of 1,1,2- | |
| CN102584581A (en) | Preparation process of hydroxy-propyl acrylate | |
| Toralles et al. | Hydrolysis of waste frying oils in subcritical water for biodiesel production by esterification using a heterogeneous catalyst | |
| CN103666769B (en) | Method for extracting fatty acid methyl ester from vegetable pitch | |
| CN114354787A (en) | Method for simultaneously detecting 3-chloropropanol ester and glycidyl ester in edible oil | |
| CN105693513B (en) | A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures | |
| Yoo et al. | Efficient and Selective Debromination of vic-Dibromides to Alkenes with NbCl 5/Indium System | |
| CN105623860B (en) | Method for reducing condensation point of biodiesel by ultraviolet irradiation method | |
| CN102584588A (en) | Method using catalysis transesterification to prepare n-amyl acetate cinnamate | |
| CN101684069B (en) | Method for enriching acetol from biomass pyrolysis liquid aqueous phase system | |
| CN110526894A (en) | A method of solketal acetate is synthesized by glycerol | |
| WO2019000819A1 (en) | METHOD FOR PREPARING LIQUID FUEL WITH γ-VALEROLACTONE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150401 Termination date: 20200422 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |