CN101747303A - Method for producing maleopimaric anhydride - Google Patents
Method for producing maleopimaric anhydride Download PDFInfo
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- CN101747303A CN101747303A CN 200910155886 CN200910155886A CN101747303A CN 101747303 A CN101747303 A CN 101747303A CN 200910155886 CN200910155886 CN 200910155886 CN 200910155886 A CN200910155886 A CN 200910155886A CN 101747303 A CN101747303 A CN 101747303A
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Abstract
The invention relates to a method for producing maleopimaric anhydride, which adopts pine resin as the raw material and utilizes self-contained turpentine as solvent. Resin acid and maleic anhydride which are changed into conjugated double bonds in the pine resin are heated to 180 to 200 DEG C, and then are separated after diene addition reaction is carried out for 2 to 4 hours, so as to obtain a white crystal, i.e. the product of maleopimaric anhydride. The method has the advantages that the production process of maleopimaric anhydride is simplified, so that the production cost is remarkably reduced; the solvents used for synthetic reaction and separation are the same solvent, i.e. the pine resin, which is non-toxic and pollution-free and can be repeatedly used after being recycled; maleopimaric anhydride is produced in the method, so that the successful solidification of epoxy resin can be realized; the prepared solidified product is superior to methyl tetrahydrophthalic anhydride in the aspect of heat resistance and strength; and simultaneously, the separated residual pine resin can be used as the raw material producing biomass fuel oil, so that the composite economic benefit is increased.
Description
Technical field
The present invention relates to a kind of method for preparing maleopimaric anhydride by rosin.
Background technology
The main chemical constitution of rosin is a terpene substances, comprises monoterpene, sesquiterpene, resinous acid and their a small amount of derivative.Resinous acid wherein is the rosiny main component, it has the multiple monobasic resinous acid isomer that contains two unsaturated double-bonds, wherein the conjugated double bond of levopimaric acid is on same ring, at normal temperatures just can with the addition reaction of maleic anhydride generation diene, and other various abietic type acids in the rosin such as abietic acid, neoabietic acid, palustric acid isomery under heating condition turn to levopimaric acid, also can obtain adducts with the maleic anhydride addition reaction.Therefore maleic anhydride is added in the equilibrium mixture that contains micro-levopimaric acid, the diene addition reaction can take place, and equilibrium mixture is constantly passed to the direction that generates micro-levopimaric acid and maleopimaric acid anhydride reactant, can obtain the maleopimaric acid anhydride adduct by such reaction.
Maleopimaric anhydride has excellent biological degradability and biocompatibility as rosin derivative, in fields such as medical science, medicine, microelectronics, environmental protection coating materials wide application prospect is arranged.CN01108250.X discloses a kind of preparation method with rosin derivative maleopimaric anhydride and the synthetic outdoor weathe resistance epoxy resin of epichlorohydrin reaction; It is the method for feedstock production maleopimaric acid tri-ester plasticizer with the maleopimaric anhydride that CN097107028.8 discloses a kind of.On structure, maleopimaric anhydride is the same with trimellitic anhydride to be tricarboxylic anhydride, has research to think that maleopimaric anhydride is the suitable surrogate of trimellitic acid 1,2-anhydride, therefore, its research and use more and more is much accounted of.
Traditional method for making of maleopimaric anhydride is to obtain rosin and turps with separating behind the rosin steam distillation, utilize the reaction of rosin and maleic anhydride to generate maleated rosin then, utilize solvent method that maleopimaric anhydride is separated from maleated rosin again, also there is research from rosin, to isolate earlier the abietic type acid, then the reported in literature of the synthetic maleopimaric anhydride of two step method route that reacts with maleic anhydride.Above-mentioned technological process of production complexity, and separate solvent for use and be generally volatile noxious solvent, so the industrialization production cost is higher, also causes a hidden trouble to environmental protection.
The present invention directly is raw material with rosin, and utilize the contained turps of rosin self to make solvent, reduced the viscosity of reaction system, shortened the production reaction times, production technique is simple, low equipment investment, and synthetic be with a kind of solvent with separating solvent for use, for the comprehensive utilization that separates the back resultant product provides favourable condition, improved overall economic efficiency.
Summary of the invention
The technical problem to be solved in the present invention is directly to be raw material production maleopimaric acid anhydride product with rosin, overcome traditional mode of production maleopimaric anhydride complex manufacturing, the shortcoming that investment of production equipment is big, building-up reactions with separate solvent for use turps, nontoxic, pollution-free, can be recycled after the recovery.Also the residue rosin after separating can be used as the raw material of producing biomass fuel simultaneously, significantly reduce production cost, improve overall economic efficiency.
The technical scheme that addresses the above problem is that this method for producing maleopimaric anhydride carries out as follows:
(1) preparation of raw material: want to buy the rosin of removing impurity and oil-containing 8%-10%, commercially pure MALEIC ANHYDRIDE, turps and Glacial acetic acid to manufacturer or chemical industry shop;
(2) addition reaction: in reactor, add 100 weight part rosin, be heated to 100-110 ℃, treat that rosin dissolves fully after, add 13～18 weight part MALEIC ANHYDRIDE again, continue to be warming up to 180～200, the reaction 2～4h, stopped reaction;
(3) producing of maleopimaric anhydride: when treating that above-mentioned reactant is cooled to 100～120 ℃, add the turps of 300～500 weight parts as solvent, leave standstill 6～12h after stirring, centrifugation upper strata solvent, get light yellow precipitate, each turps 300-500 weight part that all renews, repeat above-mentioned static, isolating operation 3 times, carry out recrystallization 2 times with 100～150 weight part Glacial acetic acid again, get white crystal, wash with water 2-3 time, 100 ℃ of oven dry promptly get the high maleopimaric acid anhydride product of purity again.
What need stress is also can utilize with the isolated residue rosin of present method, make to produce the raw material of liquid fuel oil, specific practice is: above-mentioned three separating obtained solvents merging are placed reactor, be heated to 170 ℃, behind the distillating recovering solvent, add 5 weight parts as the activity of such catalysts carclazyte, continue to be heated to 240 ℃, reaction 2h, cooling, decompress filter is removed atlapulgite, get pale brown look liquid fuel oil, the density 958kg/m3 of this oil fuel, acidity 7.5mgKOH/100ml, 20 ℃ of kinematic viscosity 47.6mm2/s, condensation point-30 ℃, 11 ℃ of cold filter clogging temperatures, cetane value 30.4,63 ℃ of flash-points, 10% steams excess carbon residue 1.9%.
The invention has the beneficial effects as follows:
Providing a kind of is the new technology approach of feedstock production maleopimaric anhydride with rosin, has simplified the production technique of maleopimaric anhydride, has reduced production cost, and the present invention to separate solvent for use turps nontoxic, pollution-free, can be recycled after the recovery.Also the residue rosin after separating can be used as the raw material of producing biomass fuel simultaneously, improve overall economic efficiency.
Embodiment
The present invention is described in further detail below in conjunction with embodiment: will want to buy each raw material, its weight part proportioning value of gained earlier, the temperature and time of reaction is listed in the table below by 7 embodiment:
Embodiment one (the temperature and time parameter value of table embodiment 1 listed raw material and weight part proportioning value thereof, reaction in the reference):
In reactor, add 100 weight part rosin, be heated to fusing, the MALEIC ANHYDRIDE that adds 13 weight parts again, continue to be warming up to 180 ℃, reaction 2h promptly ends, when treating that this reactant is cooled to 100 ℃, add the turps of 300 weight parts, leave standstill 6h after stirring, centrifugation upper strata solvent as solvent, stay light yellow precipitate, so repeat above-mentioned operation totally 3 times, all add new turps 300 weight parts at every turn, leave standstill 6h after stirring equally, centrifugation upper strata solvent, the light yellow precipitate that will stay after three dissolvings is carried out recrystallization with 100 weight part Glacial acetic acid at last, get white crystal, wash with water 2-3 time, 100 ℃ of oven dry are the high maleopimaric acid anhydride product of purity.Again above-mentioned three separating obtained solvents merging are placed reactor, be heated to 160 ℃, behind the distillating recovering solvent (turps), get the rosin industrial wood waste, can be used for preparing the raw material of biological pesticide and biomass fuel.
All the other embodiment 2-7, the raw material shown in the embodiment sequence of epiphase correspondence, proportioning weight part value, temperature of reaction and time conditions in the reference all can make the maleopimaric acid anhydride product with embodiment 1 same procedure.Respectively there are some difference the proportioning raw materials value of seven embodiment and temperature of reaction and time, this can determine to react whether fully with speed of response etc., the turpentine oil content dissolves several times with separating also to be taken all factors into consideration and decides from improving percentage extraction and work efficiency, therefore also can divide secondary or four addings.Among seven embodiment, preferred with embodiment 2,4.Every embodiment all finishes under the condition of normal pressure of reactor.
This maleopimaric anhydride is a white crystal, acid number 416.5mg/g, theoretical acid number 420mg/g.Product is as follows through results of IR: 3414cm
-1For-COOH-OH stretches and absorbs, 2952cm
-1And 2869cm
-1Absorb 1840cm for aliphatic CH is flexible
-1And 1771cm
-1Be the flexible absorption of acid anhydrides C=O, 1689cm
-1Be the flexible absorption of the C=O of COOH, 1226cm
-1Be the flexible absorption of the C-O of COOH, 1085cm
-1Be the flexible absorption of acid anhydrides C-O-C, 945cm
-1And 924cm
-1Crooked absorption of O-H for COOH meets the reported in literature value.
Is 1: 0.8 with this maleopimaric anhydride by equivalence ratio with Resins, epoxy 618, under 120 ℃ of 5h conditions, can realize the successful curing of this maleopimaric anhydride to Resins, epoxy 618.Thermotolerance and intensity to this cured product are analyzed, and comparison shows that with the thermotolerance and the intensity of methyl tetrahydro phthalic anhydride and Resins, epoxy 618 cured products, the decomposition temperature of maleopimaric anhydride is 371.5 ℃, than 365.5 ℃ high 6 ℃ of methyl tetrahydro phthalic anhydride decomposition temperatures; The average shear intensity of test gained maleopimaric anhydride is 17.30Mpa, average shear intensity than methyl tetrahydro phthalic anhydride is the high 3.74Mpa of 13.56Mpa, illustrate that this product can replace methyl tetrahydro phthalic anhydride as epoxy curing agent usefulness, and the gained cured product is being better than methyl tetrahydro phthalic anhydride aspect thermotolerance and the intensity.
Claims (1)
1. method for producing maleopimaric anhydride is characterized in that carrying out as follows:
(1) raw material is prepared: want to buy the rosin of removing impurity and oil-containing 8%-10%, commercially pure MALEIC ANHYDRIDE, turps and Glacial acetic acid to manufacturer or chemical industry shop;
(2) addition reaction: in reactor, add 100 weight part rosin, be heated to 100-110 ℃, treat that rosin dissolves fully after, add 13～18 weight part MALEIC ANHYDRIDE again, continue to be warming up to 180～200, the reaction 2～4h, stopped reaction;
(3) producing of maleopimaric anhydride: when treating that above-mentioned reactant is cooled to 100～120 ℃, add the turps of 300～500 weight parts as solvent, leave standstill 6～12h after stirring, centrifugation upper strata solvent, get light yellow precipitate, each turps 300-500 weight part that all renews, repeat above-mentioned static, isolating operation 3 times, carry out recrystallization 2 times with 100～150 weight part Glacial acetic acid again, get white crystal, wash with water 2-3 time, 100 ℃ of oven dry promptly get the high maleopimaric acid anhydride product of purity again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200910155886 CN101747303A (en) | 2009-12-29 | 2009-12-29 | Method for producing maleopimaric anhydride |
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| CN 200910155886 CN101747303A (en) | 2009-12-29 | 2009-12-29 | Method for producing maleopimaric anhydride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN103254161A (en) * | 2011-12-21 | 2013-08-21 | 东莞市信诺橡塑工业有限公司 | Synthesis method of gum rosin derivative maleopimaric acid dianhydride |
| CN109467674A (en) * | 2018-08-14 | 2019-03-15 | 南京大学 | A kind of resveratrol base fire retarding epoxide resin and preparation method thereof |
| CN113416492A (en) * | 2021-07-13 | 2021-09-21 | 桂林兴松林化有限责任公司 | Production process of rosin modified resin for hot melt adhesive production |
-
2009
- 2009-12-29 CN CN 200910155886 patent/CN101747303A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254161A (en) * | 2011-12-21 | 2013-08-21 | 东莞市信诺橡塑工业有限公司 | Synthesis method of gum rosin derivative maleopimaric acid dianhydride |
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN109467674A (en) * | 2018-08-14 | 2019-03-15 | 南京大学 | A kind of resveratrol base fire retarding epoxide resin and preparation method thereof |
| CN109467674B (en) * | 2018-08-14 | 2022-02-08 | 南京大学 | Resveratrol-based flame-retardant epoxy resin and preparation method thereof |
| CN113416492A (en) * | 2021-07-13 | 2021-09-21 | 桂林兴松林化有限责任公司 | Production process of rosin modified resin for hot melt adhesive production |
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Open date: 20100623 |