CN1250492C - Preparation of pure longifolene - Google Patents
Preparation of pure longifolene Download PDFInfo
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- CN1250492C CN1250492C CN200410044911.0A CN200410044911A CN1250492C CN 1250492 C CN1250492 C CN 1250492C CN 200410044911 A CN200410044911 A CN 200410044911A CN 1250492 C CN1250492 C CN 1250492C
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- longifolene
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- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 241000779819 Syncarpia glomulifera Species 0.000 claims abstract description 21
- 239000001739 pinus spp. Substances 0.000 claims abstract description 21
- 229940036248 turpentine Drugs 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims description 19
- 238000005516 engineering process Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 18
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 18
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 18
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 18
- 239000003456 ion exchange resin Substances 0.000 description 12
- 229920003303 ion-exchange polymer Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 9
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000019687 Lamb Nutrition 0.000 description 3
- 235000011609 Pinus massoniana Nutrition 0.000 description 3
- 241000018650 Pinus massoniana Species 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229930004725 sesquiterpene Natural products 0.000 description 3
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 3
- 235000017339 Pinus palustris Nutrition 0.000 description 2
- 241000204936 Pinus palustris Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 235000005205 Pinus Nutrition 0.000 description 1
- 241000218602 Pinus <genus> Species 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000186 gas chromatography-infrared spectroscopy Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation technique of high-purity longifolene, which comprises the following steps: step 1: heavy turpentine, water and strong acidic cation-exchange resin with macropore adsorption are mixed according to the mass ratio of 100: (1 to 100): (1 to 100); step 2: mixture obtained in step 1 is stirred at 10 DEG C to 100 DEG C for a reaction for 0.5 to 6 hours, and the solid resin is removed by filtration after the reaction is finished; step 3: filter liquor obtained from the step 2 is distilled by pressure reduction to collect a fraction with the boiling point below 110 DEG C (5 mmHg), and the fraction approximately accounts for 80% to 90% of the distilled raw materials; step 4, the fraction obtained from the step 3 is fractionated by pressure reduction again, and the products of the high-purity longifolene with different specifications and the longifolene content from 85% to 98% can be obtained according to the difference of the boiling point of the intercepted fraction.
Description
One. technical field
The present invention relates to a kind of preparation technology of high-purity natural spices sesquiterpenoid longifolene, especially obtain the method for high purity longifolene in the sesquiterpene mixture from heavy turpentine (turps last running is hereinafter to be referred as heavy oil).
Two. background technology
Longifolene (Longifo1ene CAS No.475-20-7) is a kind of nature that extensively is present in, and present a kind of sesquiterpene of output maximum in the world [referring to: P.K.Jadhay et alJ.Sci.Ind.Res.39 (1980) 36～43], produce about 20,000 tons per year.Longifolene is a kind of important natural perfume and fine chemical material, and market has a wide range of applications.Therefore, the technology of preparing of high purity longifolene receives much concern.India uses micro-organism treatment process, separates obtaining containing 81～83% medium purity longifolene from longleaf pine rosin.Contain in the Pinus massoniana Lamb rosin of China abundant longifolene composition [referring to Liang Zhiqin, purple flourish chemistry of forest product of ginger and industry 1 (2) 40 (1981); The scientific and technological communication 1986 (3) 2～6 of Jiang Fengchi woodsization].But except that the longifolene that contains about 60%, also contain β-caryophyllene of 7～20%, and two compound physical performances are quite similar, abut against together in the chromatographic separation collection of illustrative plates in the Pinus massoniana Lamb heavy oil, are difficult to it be separated with the conventional distillation method.At present, can only to obtain content be 72% longifolene to the rectification process that domestic usefulness is traditional.Bibliographical information [referring to chemistry of forest product and industry 2 (17) 31 (1997) such as: Chen Changfa], human eluents such as Chen Changfa (CS type) are reduced to the β-caryophyllene in the heavy oil below 0.8%, and obtaining content through fractionation again is 80%, 85%, 90% longifolene.But the composition of eluent and chemical ingredients and chemical structure are not reported, do not see the product of its explained hereafter so far on market yet, and there are insoluble problem in possible its elution processes and quality product.Therefore, the new preparation process of Development and Production high purity longifolene is most important.
Three. technology contents
The turps heavy oil that the present invention obtains when adopting rosin process plants rosin is raw material. this fraction mainly contains the sesquiterpene component of rosin, and wherein longifolene is 50～65%, β-caryophyllene 1～30%.The present invention aims to provide a kind of preparation technology who isolates the high purity longifolene from heavy turpentine, and the longifolene that this technology also can be used in the heavy turpentine that all other Pinus classes produce separates, as the preparation of high purity longifolene in the longleaf pine rosin.
Technical scheme of the present invention is as follows:
A kind of preparation technology of high purity longifolene, it comprises the following steps:
Step 1, with heavy turpentine, water and macroporous absorption storng-acid cation exchange resin, be 100: 1～100: 1～100 mixed by mass ratio,
Step 2, with the mixture of step 1 gained under 10～100 ℃, stirring reaction 0.5-6 hour, reaction was finished after-filtration and is removed the solids resin,
Step 3, the filtrate of step 2 gained is carried out underpressure distillation, collect the cut that boiling point is lower than 110 ℃ (5mmHg), this cut accounts for and is distilled 80～90% of raw material,
Step 4, the cut of step 3 gained is carried out vacuum fractionation again,, can obtain containing the high purity longifolene product of longifolene 85%～98% different size according to the boiling point fraction difference of intercepting.
Above-mentioned technology, before the step 3 underpressure distillation, if the water yield that adds of step 1 is more, can first standing demix, remove water layer, then three underpressure distillation set by step.
Above-mentioned technology, the pressure of underpressure distillation is absolute pressure 3～50mmHg in step 3 or the step 4.
Above-mentioned technology also can be used fixed bed or fluidized-bed catalytic reactor instead and be carried out, and its step is as follows:
Step 1, the macroporous absorption storng-acid cation exchange resin filled out be placed in fixed bed or the fluidized-bed catalytic reactor, keep catalytic reactor temperature at 10～100 ℃,
Step 2, with heavy turpentine and water press mass ratio 100: 1～100 mixed,
Step 3, with the mixture of step 2 gained 10～100 ℃ by described fixed bed of step 1 or fluidized-bed catalytic reactor, mixture is 5～8 minutes by the residence time of beds,
Step 4, with the reaction mixture underpressure distillation of step 3 gained, collect the cut that boiling point is lower than 110 ℃ (5mmHg), this cut accounts for and is distilled 80～90% of raw material,
Step 5, the cut of step 4 gained is carried out vacuum fractionation again,, can obtain containing the high purity longifolene product of longifolene 85%～98% different size according to the boiling point fraction difference of intercepting.
Above-mentioned technology, before the step 4 underpressure distillation, if the water yield that adds of step 2 is more, can first standing demix, remove water layer, then four underpressure distillation set by step.
Above-mentioned technology, the pressure of underpressure distillation is absolute pressure 3～50mmHg in step 4 or the step 5.
Advantage of the present invention: (1) the present invention makes longifolene separate with β-caryophyllene with reacting the isolating method in back earlier, solved because two compound physical properties are similar and be difficult to separate, thereby be difficult to obtain the technical problem of high purity longifolene, can obtain longifolene content and be the product of 85～98% different size.(2) the present invention is in when reaction, selection be hydration reaction, only add deionized water as reactant, kept the natural characteristic of raw material sources and the natural quality of product longifolene, do not produce any bad side reaction.(3) the hydration reaction catalyzer that uses among the present invention is the macroporous absorption storng-acid cation exchange resin, is solid, with the reaction product separate easily, does not add any solvent and auxiliary agent, does not need neutralization, washing.Catalyzer can use repeatedly, the finished product is not polluted, and is a kind of eco-friendly process for cleanly preparing.(4) the present invention make the β-caryophyllene reaction generation β-caryophyllenol in the heavy turpentine, and longifolene does not react with the method for hydration reaction.And there are the difference of very big thermodynamic property in β-caryophyllenol and longifolene, thereby easily they are separated.So when obtaining the high purity longifolene, also can obtain another important product-β-caryophyllenol, longifolene composition and other effective ingredients in the natural turps are fully utilized, increased economic benefit greatly.
Four. embodiment
The proportion of longifolene is D
300.9284 refractive index is N
301.483 the specific rotation value is [α]
20+ 41.52, the longifolene of following examples gained is analyzed with GC-MS and GC-IR, and wherein the MS of longifolene component, IR and document is consistent, analyzes its content with gas chromatographic analysis and normalization method.The condition of gas-chromatography is: chromatographic column: quartz capillary OV-1010.30 μ m * 0.25mm * 30m, and the vaporizer temperature: 250 ℃, detector temperature: 250 ℃, splitting ratio: 90: 1, flow: H
2: 40mL/min; Air:450mL/min; N
2: 20mL/min, temperature programming: 120 ℃ of (1mi n) → 4 ℃/mi n → 200 ℃ (1min).
Embodiment 1.
With 100 parts of (quality, down with) contain the heavy turpentine that obtains the rosin of longifolene composition from Pinus massoniana Lamb etc., add 1 part of water, add 1 part of macroporous absorption strong-acid ion exchange resin (CD-550 type, the Hangzhou resin processing plant that wins honour for produces), 100 ℃ of reactions 6 hours down.Make wherein that β-caryophyllene component is generated β-caryophyllenol by hydration reaction, and the content of β-caryophyllene is reduced to below 1%.After reaction is finished, the solids removed by filtration resin, underpressure distillation, collect the cut that boiling point is lower than 110 ℃ (5mmHg), totally 88 parts (100 parts are distilled) carries out underpressure distillation again with the cut that steams then under the pressure of 5mmHg, obtain longifolene content and be 85% 11 parts, content is 90% 22 parts, and content is 95% 36 parts, and content is 12 parts (to distill 100 parts) of 98%.
Embodiment 2.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 10 parts of water, add 10 parts of macroporous absorption strong-acid ion exchange resin (D072 types, Chemical Plant of Nankai Univ. produces), 90 ℃ of reactions 5 hours, make wherein that β-caryophyllene component is generated β-caryophyllenol by hydration reaction, and the content of β-caryophyllene is reduced to below 1%.After reaction was finished, first solids removed by filtration resin again with the filtrate standing demix, discarded the unreacted water layer of lower floor, and following steps are with embodiment 1, and the result is with embodiment 1.
Embodiment 3.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 20 parts of water, add 20 parts of macroporous absorption strong-acid ion exchange resins [D002 type catalyst resin (dry hydrogen resin), Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces], 80 ℃ of reactions 4 hours, following steps are with embodiment 2, and the result is with embodiment 1.
Embodiment 4.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 30 parts of water, add 37 parts of macroporous absorption strong-acid ion exchange resins (Shanghai Resin Factory Co., Ltd.'s production), 70 ℃ of reactions 3 hours.Following steps are with embodiment 2, and the result is with embodiment 1.
Embodiment 5.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 40 parts of water, add 48 parts of macroporous absorption strong-acid ion exchange resins (D001 type, TianXing, Bengbu resin company limited produces), 60 ℃ of reactions 2 hours.Following steps are with embodiment 2, and the result is with embodiment 1.
Embodiment 6.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 50 parts of water, add 51 parts of macroporous absorption strong-acid ion exchange resins (D001 type, the precious grace chemical industry in Cangzhou company limited produces), 50 ℃ of reactions 1 hour.Following steps are with embodiment 2, and its result is with embodiment 1.
Embodiment 7.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 60 parts of water, add 63 parts of macroporous absorption strong-acid ion exchange resins (NKC-9 type dry hydrogen resin, Chemical Plant of Nankai Univ. produces), 40 ℃ of reactions 0.8 hour.Following steps are with embodiment 2, and its result is with embodiment 1.
Embodiment 8.
Add 3.3 parts of water by the heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition, feed 70 parts of macroporous absorption strong-acid ion exchange resin (the D001 types that are equipped with behind the thorough mixing, the production of Cangzhou precious grace chemical industry company limited) fixed-bed reactor, this reactor jacket heating, constant temperature is at 90 ℃, and reactant is 5.5 minutes in the residence time of resin layer.After reaction mixture flowed out from fixed-bed reactor, following treatment step was with embodiment 1, and its result is basically with embodiment 1.
Embodiment 9.
Add 80 parts of water by the heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition, 90 parts of macroporous absorption strong-acid ion exchange resins (NKC-9 type dry hydrogen resin is equipped with in ℃ feeding of thorough mixing post-heating to 90, Chemical Plant of Nankai Univ.'s production) fluidized-bed reactor, this reactor jacket heating, constant temperature is at 90 ℃, and flow is 16L/h, and circulation fed 5 minutes, following treatment step is with embodiment 2, and its result is similar to embodiment 1.
Embodiment 10.
Add 88 parts of water by the heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition, feed behind the thorough mixing 92 parts of macroporous absorption strong-acid ion exchange resins (NKC-9 type dry hydrogen resin is housed, Chemical Plant of Nankai Univ.'s production) fixed-bed reactor, this reactor jacket heating, constant temperature is at 80 ℃, and reactant is 7.2 minutes in the residence time of resin layer, after reaction mixture flows out from fixed-bed reactor, following treatment step is with embodiment 2, and its result is basically with embodiment 1.
Embodiment 11.
The heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition is added 100 parts of water, add 100 parts of macroporous absorption strong-acid ion exchange resins (D001-cc type, Chemical Plant of Nankai Univ. produces), 100 ℃ of reactions 0.5 hour.Following steps are with embodiment 2, and its result is with embodiment 1.
Embodiment 12.
Add 20 parts of water by the heavy turpentine that obtains in 100 parts the rosin that contains the longifolene composition, 40 parts of macroporous absorption strong-acid ion exchange resins (NKC-9 type dry hydrogen resin is equipped with in ℃ feeding of thorough mixing post-heating to 80, Chemical Plant of Nankai Univ.'s production) fluidized-bed reactor, this reactor jacket heating, constant temperature is at 80 ℃, and flow is 50L/h, and circulation fed 6 minutes, following treatment step is with embodiment 2, and its result is similar to embodiment 1.
Claims (6)
1. the preparation technology of a longifolene is characterized in that it comprises the following steps:
Step 1, with heavy turpentine, water and macroporous absorption storng-acid cation exchange resin, be 100: 1～100: 1～100 mixed by mass ratio,
Step 2, with the mixture of step 1 gained under 10～100 ℃, stirring reaction 0.5-6 hour, reaction was finished after-filtration and is removed the solids resin,
Step 3, the filtrate of step 2 gained is carried out underpressure distillation, collects the cut that boiling point is lower than 110 ℃/5mmHg,
Step 4, the cut of step 3 gained is carried out vacuum fractionation again, obtain the longifolene product.
2. technology according to claim 1 is characterized in that: before the step 3 underpressure distillation, if the water yield that step 1 adds is more, first standing demix is removed water layer, then three underpressure distillation set by step.
3. technology according to claim 1 is characterized in that: the pressure of underpressure distillation is absolute pressure 3～50mmHg in step 3 or the step 4.
4. technology according to claim 1 is characterized in that: when reaction was carried out with fixed bed or fluidized-bed catalytic reactor, its step was as follows:
Step 1, the macroporous absorption storng-acid cation exchange resin filled out be placed in fixed bed or the fluidized-bed catalytic reactor, keep catalytic reactor temperature at 10～100 ℃,
Step 2, with heavy turpentine and water press mass ratio 100: 1～100 mixed,
Step 3, with the mixture of step 2 gained 10～100 ℃ by described fixed bed of step 1 or fluidized-bed catalytic reactor, mixture is 5～8 minutes by the residence time of beds,
Step 4, with the reaction mixture underpressure distillation of step 3 gained, collect the cut that boiling point is lower than 110 ℃/5mmHg,
Step 5, the cut of step 4 gained is carried out vacuum fractionation again, obtain the longifolene product.
5. technology according to claim 4 is characterized in that: before the step 4 underpressure distillation, if the water yield that step 2 adds is more, first standing demix is removed water layer, then four underpressure distillation set by step.
6. technology according to claim 4 is characterized in that: the pressure of underpressure distillation is absolute pressure 3～50mmHg in step 4 or the step 5.
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| CN102952643A (en) * | 2012-11-15 | 2013-03-06 | 梧州市松桦化学品有限公司 | Longifolene perfume material and preparation method thereof |
| CN103449954B (en) * | 2013-08-27 | 2015-04-15 | 梧州市松桦化学品有限公司 | Preparation method of high-purity longifolene |
| CN104130096B (en) * | 2014-07-07 | 2016-03-09 | 广西壮族自治区林业科学研究院 | A kind of method being continuously separated high-purity longifolene from heavy turpentine |
| CN104193579A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Purification method for longifolene |
| CN104909976A (en) * | 2015-05-27 | 2015-09-16 | 梧州市嘉盈树胶有限公司 | Longifolene purification method |
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