CN102585192A - Biologic polycarbonate and preparation method thereof - Google Patents

Biologic polycarbonate and preparation method thereof Download PDF

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CN102585192A
CN102585192A CN2011104581490A CN201110458149A CN102585192A CN 102585192 A CN102585192 A CN 102585192A CN 2011104581490 A CN2011104581490 A CN 2011104581490A CN 201110458149 A CN201110458149 A CN 201110458149A CN 102585192 A CN102585192 A CN 102585192A
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fatty acid
unsaturated fatty
natural plant
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CN102585192B (en
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蒋剑春
王奎
陈洁
李静
应浩
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Institute of Chemical Industry of Forest Products of CAF
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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Abstract

The invention provides a biologic polycarbonate and a preparation method thereof. The biologic polycarbonate is obtained by polymerizing biologic epoxy fatty acid ester serving as a raw material and CO2 gas, the yield is more than or equal to 70 percent, the number-average molecular weight is 11,000 to 30,000, and the molecular weight distribution is 1.10 to 1.74; and the biologic epoxy fatty acid ester is obtained by hydrolyzing, freezing and separating unsaturated fatty acid ester from natural vegetable fat and then performing epoxidation, or obtained by direct epoxidation of the natural vegetable fat. The renewable natural vegetable fat and the greenhouse gas CO2 are used as raw materials, so the method is environment-friendly, low in cost and simple and feasible in process operation, the solvent and the catalyst can be efficiently recycled, and the method is environment-friendly and suitable for industrialized production.

Description

Biological poly carbonic ether and preparation method thereof
Technical field
The invention belongs to the technology of polycarbonate synthesis, particularly a kind of biological poly carbonic ether by natural plant grease preparation and preparation method thereof.
Background technology
Carbonic acid gas (CO 2) be that to cause the main gas of global greenhouse effect be again abundant, nontoxic, not flammable, the cheap and reproducible resources of a kind of reserves.To CO 2Resource reasonably develops, and meets the long term growth planning of country, has important Significance for Environment and social value.
CO 2Recycling---like rare gas element, refrigerant, beverage gas, the gas fertile and chemistry utilize---carbon source in organic solvent and the chemical reaction that mainly comprises the physics utilization.With CO 2Be carbon source, through chemical process synthesis of chemicals such as urea, alcohol, acid, polyester etc. become CO 2Focus in the recycling and trend.Wherein, CO 2With synthesis of epoxy compounds prepared in reaction polycarbonate, still be that the angle of environment is considered no matter from economy, all be the chemical process of tool using value and prospect.
Domestic and international present Research:
The reported first CO of Inoue research group of Tokyo Univ Japan in 1969 2And propylene oxide (PO) is the ZnEt of 1:1 in mol ratio 2And H 2Alternating copolymerization generates and gathers propylene carbonate under the catalysis of O.After this, the research of carbonic acid gas and epoxy compounds copolymerization is worldwide extensively carried out.
The alternating copolymerization of carbonic acid gas and epoxy compounds has been studied by Meng seminar.Beckman seminar and Darensbourg seminar, the alternating copolymerization reaction product weight-average molecular weight of cyclohexene oxide for preparing respectively and carbonic acid gas can reach 252000 g/mol.CO has studied in Coates seminar 2With the asymmetric ring-opening polymerization of cyclohexene oxide, under the reaction pressure of 0.69MPa, can to obtain molecular weight be 21300 to reaction 2h, and MWD is the polycarbonate of 1.07 alternating structure.Sugimoto etc. have studied cyclohexene oxide and CO 2Copolymerization, at 80 ℃, 5MPaCO 2Pressure is reaction 24h down, can obtain carbonic ether chain link content greater than 99%, and number-average molecular weight is 14500 g/mol, and MWD is 1.13 polycarbonate.Qin etc. improve technology, at 25 ℃, and 2MPaCO 2Pressure is reaction 5h down, can obtain carbonic ether chain link content greater than 99%, and number-average molecular weight is 48000 g/mol, and MWD is 1.17 polycarbonate.Above-mentioned technology is the feedstock production polycarbonate with petroleum-based epoxy compounds all, makes the polycarbonate with high number-average molecular weight and distribution of low molecular weight.
It is the research of feedstock production cyclic carbonate that Tamami etc. and the Li Zhen of Shanxi Coal-Chemical Inst., Chinese Academy of Sciences honor etc. have successively been carried out with the epoxy soybean oil per capita: epoxy soybean oil and CO 2At 1MPa, under 120 ℃, reaction 20h makes cyclic carbonate, and then is used to prepare polyurethane material, owing to can't realize the polymerization of cyclic carbonate, therefore can't prepare and has H.T. and high-molecular weight polycarbonate material.
The present existing defective of technology:
(1) all to select petroleum base epoxy compoundss such as propylene oxide, cyclohexene oxide and epoxy chloropropane for use mostly be the feedstock production polycarbonate to existing processes; Because fossil oils such as oil are non-renewable; Therefore select for use the petroleum base epoxy compounds not meet the demand for development of environmental protection low-carbon (LC), do not have the application prospect of sustainability.
(2) existing epoxy compounds with natural products such as natural plant grease or glycerine and resins is the technology of raw material; Because the macromolecular structure of natural product, make sterically hindered greatlyyer, the epoxy bond activity is lower; More difficult open loop generates polycarbonate; The cyclic carbonates that generate can only be applied to the composite etc. of polyurethane material more, can't prepare to have excellent in toughness and high-molecular weight chain polycarbonate.
Summary of the invention
For mostly the polycarbonate that solves the prior art existence is petroleum base; The problem of not enough environmental protection; The present invention provides a kind of biological poly carbonic ether and preparation method thereof; Raw material natural reproducible, with low cost, technology is workable, solvent and catalyst recovery are easy, and product performance are good and commercial viability is high prepares the method for biological poly carbonic ether by natural plant grease.
Technical scheme of the present invention is: a kind of biological poly carbonic ether is raw material and CO with the bio-based epoxy aliphatic ester 2The gas polymerization obtains the biological poly carbonic ether, productive rate>=70%, and number-average molecular weight is 11000 ~ 30000, MWD is 1.10 ~ 1.74; Epoxidation obtains described bio-based epoxy aliphatic ester in order to be gone out behind the unsaturated fatty acid ester again by natural plant grease elder generation hydrolysis subzero fractionation, is perhaps obtained by the direct epoxidation of natural plant grease.
Described natural plant grease is arbitrary in tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or the Oleum Gossypii semen.
A kind of method for preparing described biological poly carbonic ether; Mol ratio according to bio-based epoxy aliphatic ester and catalyzer is: the ratio of 1:0.01～1:0.005; Bio-based epoxy aliphatic ester, solvent and catalyzer are stirred, be warming up to 80～140 ℃, oxygen free condition feeds CO down 2Gas to 1.0～7.0MPa keeps reaction pressure and temperature, react to the reaction system oxirane value no longer to change, reaction solution with hot wash after, get the oil phase underpressure distillation, remove residual solvent, the biological poly carbonic ether.
Described bio-based epoxy aliphatic ester goes out behind the unsaturated fatty acid ester again by natural plant grease elder generation hydrolysis subzero fractionation that epoxidation obtains, and concrete steps are: the first step, and the hydrolysis subzero fractionation of natural plant grease: natural plant grease in molar ratio: sodium hydroxide is 1:3 ~ 1:5; The ratio that low-carbon alcohol is excessive is blended in natural plant grease, low-carbon alcohol and aqueous sodium hydroxide solution under the reflux temperature and reacts, after reaction finishes; Conditioned reaction system pH to 3～4; Standing demix mixes sealing with low-carbon alcohol by mass ratio 1:3～5 with the supernatant liquid of telling, earlier at 0～1 ℃ of precooling 2h; The back is freezing 2h under-20～-15 ℃; Cross and filter clear filtrate, the clear filtrate underpressure distillation gets unsaturated fatty acid ester;
Second step; The epoxidation of unsaturated fatty acid ester: the mol ratio according to unsaturated fatty acid ester and formic acid is the ratio of 1～2:1; Unsaturated fatty acid ester, formic acid and epoxidation catalyst are mixed stirring be warming up to 50～70 ℃; The dropping mass concentration is 30～50% ydrogen peroxide 50, drips off in 2 hours, continues insulation reaction to reaction system oxirane value and no longer changes; The quality percentage that the epoxidation catalyst consumption accounts for the unsaturated fatty acid ester consumption is 0.5%～5%, and the ydrogen peroxide 50 consumption accounts for 30%～60% of unsaturated fatty acid ester consumption; After above-mentioned reaction finishes, filter, regulate filtrating pH value to 6.0～6.9, washing, behind the standing demix, get the upper oil phase drying under reduced pressure after, get the bio-based epoxy aliphatic ester.
The described low-carbon alcohol of the first step is arbitrary in methyl alcohol, ethanol, propyl alcohol, the Virahol.
Described bio-based epoxy aliphatic ester is obtained by the direct epoxidation of natural plant grease, and concrete steps are: be after the ratio of 1 ~ 2:1 mixes natural plant grease and formic acid in the mol ratio of natural plant grease and formic acid, add the quality percentage that accounts for the natural plant grease consumption while stirring and be 0.5 ~ 5% epoxidation catalyst; Mechanical stirring is warming up to 50 ~ 70 ℃ after evenly, and it is 30 ~ 50% ydrogen peroxide 50 that constant speed drips the mass concentration that accounts for natural plant grease consumption 30 ~ 60%, drips off in 2 hours; Continued insulation reaction 2 ~ 5 hours; Reaction finishes postcooling to room temperature, filters, and regulates filtrating pH value to 6.0～6.9; Distilled water wash is used in the back; Behind the standing demix, get the upper oil phase drying under reduced pressure after, the bio-based epoxy aliphatic ester.
Described epoxidation catalyst is S 2O 8 2-/ mesoporous Z rO 2Catalyzer, S 2O 8 2-/ mesoporous T iO 2Catalyzer, S 2O 8 2-/ mesoporous S nO 2Arbitrary in catalyzer or the nickel Schiff's base/cellular silica.
Described solvent is THF, N, dinethylformamide, N, arbitrary in N-DMSO 99.8MIN., the N-N-methyl-2-2-pyrrolidone N-.
Described catalyzer is the arbitrary of pentanedioic acid zinc catalyst, pimelic acid zinc catalyst, Zinc dibenzoate catalyzer, diimine zinc catalyst, porphyrin chromium, Cobalt Porphyrin and SalenCr catalyzer.
Beneficial effect:
1, the inventive method is with natural plant grease and CO 2Be raw material, separate through hydrolysis earlier that obtain highly purified unsaturated fatty acid ester, the initial ring oxidizing reaction prepares highly purified epoxy aliphatic ester again, last and CO to the crude vegetal fat raw material 2Polymerization reaction take place, preparation biological poly carbonic ether.Selected raw material natural plant grease and CO 2Be the natural green renewable resources, and with low cost, product performance are good, environmental friendliness, commercial viability is strong.
2, the inventive method is passed through the hydrolysis of crude vegetal fat raw material earlier; Obtain croude fatty acids, utilize sfas and the unsaturated fatty acids solvability difference in low-carbon alcohol solution then, filter through freezing; Obtain highly purified unsaturated fatty acids; Greatly reduce the sterically hindered of polyreaction, increased the proportion of epoxy bond, thereby be beneficial to the generation of polyreaction.
3, the inventive method does not have particular requirement to the crude vegetal fat raw material; The natural plant grease that can be adapted to various raw material sources is like tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or cottonseed wet goods; Raw material sources are extensive; Greatly reduced the industrial cost of biological poly carbonic ether, and product have good snappiness and biodegradability.
4, the inventive method technology is workable, obtains the epoxy aliphatic ester than high epoxy value through the hydrolysis of natural plant grease and the epoxidation of peroxy acid, satisfies the needs of crude vegetal fat raw material and produce market.
But environmental friendliness is reused in 5, all high efficiente callbacks of the inventive method solvent for use and catalyzer.
6, the inventive method adopts WATER-WASHING METHOD refining reaction product, and operation is simple and feasible, and the solvent for use recovery is high, non-environmental-pollution, and commercial viability is high.
7, the present invention's bio-based epoxy aliphatic ester that also can adopt the direct epoxidation of natural plant grease to obtain is the feedstock production polycarbonate.
Description of drawings
Fig. 1 is the GC-MS spectrogram that separates after the unsaturated fatty acids esterification obtain, and staple is oleic acid and linolic acid, also contains a spot of sfas, and unsaturated fatty acid content is more than 90%.
Fig. 2 is the IR spectrogram contrast of the biological poly carbonic ether of unsaturated fatty acid ester, epoxy aliphatic acid methyl ester and generation, through after the epoxidation reaction, at 819 cm -1And 843cm -1The charateristic avsorption band of epoxy bond appears in the place, and through after the polyreaction, the charateristic avsorption band of epoxy bond disappears, at 1810 cm -1The charateristic avsorption band of carbonic acid ester bond appears in the place, shows the epoxy bond and the CO of epoxy aliphatic ester 2Polymerization generates the biological poly carbonic ether.
Fig. 3 is the present invention prepares the method for biological poly carbonic ether with natural plant grease a schema.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Biological poly carbonic ether among the present invention is synthetic by following raw material:
Natural plant grease: arbitrary in tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or the Oleum Gossypii semen, no rank requirement.
CO 2: commercially available.
Epoxidation catalyst: laboratory self-control, the preparation method is with reference to Yin H L, Tan Z Y, Liao Y T, et al. Environ Radioactivity, 2006,87 (2): 227-235.
Polymerizing catalyst: laboratory self-control, preparing method's reference: Scott D, David R, Emil B, et al. Journal of American Chemical Science, 2002,124,14284-14285; Donald J, Jacob R, Jason C. Inorganic Chemistry, 2002,41,973-980; Donald J, Jason C. Journal of American Chemical Science, 2002,124,6335-6342; Meng Y Z, Du L C, Tjong S C, et al. Journal of Polymer Science. Part A, Polymer Chemistry, 2002,40:3579-3591.
Solvent (alcohol, acid, urea): technical grade.
A kind of biological poly carbonic ether is raw material and CO with the bio-based epoxy aliphatic ester 2The gas polymerization obtains the biological poly carbonic ether, productive rate>=70%, and number-average molecular weight is 11000 ~ 30000, MWD is 1.10 ~ 1.74; Epoxidation obtains described bio-based epoxy aliphatic ester in order to be gone out behind the unsaturated fatty acid ester again by natural plant grease elder generation hydrolysis subzero fractionation, is perhaps obtained by the direct epoxidation of natural plant grease.Described natural plant grease is arbitrary in tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or the Oleum Gossypii semen.
A kind of method for preparing described biological poly carbonic ether; Mol ratio according to bio-based epoxy aliphatic ester and catalyzer is: the ratio of 1:0.01～1:0.005; Bio-based epoxy aliphatic ester, solvent and catalyzer are stirred, be warming up to 80～140 ℃, oxygen free condition feeds CO down 2Gas to 1.0～7.0MPa keeps reaction pressure and temperature, react to the reaction system oxirane value no longer to change, reaction solution with hot wash after, get the oil phase underpressure distillation, remove residual solvent, the biological poly carbonic ether.
A kind of preparation method of bio-based epoxy aliphatic ester, below be behind first hydrolysis, the subzero fractionation again epoxidation and then and the concrete synthesis step of carbonic acid gas polymeric:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of natural plant grease and sodium hydroxide is 1:1～1:5, the ratio that low-carbon alcohol is slightly excessive; Add there-necked flask with low-carbon alcohol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature generally at 60 ℃～80 ℃ following dropwise reaction 0.5h～3h, is incubated 1 h～2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with low-carbon alcohol by mass ratio 1:3～1:5, and in 0 ℃～1 ℃ precooling and-20 ℃～-15 ℃ each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims low-carbon alcohol.Described natural plant grease is arbitrary in tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or the Oleum Gossypii semen, and described low-carbon alcohol is arbitrary in methyl alcohol, ethanol, propyl alcohol, the Virahol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid adding of 3:1～5:1 has churned mechanically there-necked flask, after the mixing; Add the quality percentage account for the unsaturated fatty acid ester consumption while stirring and be 1%～10% catalyzer, mechanical stirring is warming up to 50～70 ℃ after evenly, and dripping 30%～60% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30～50% ydrogen peroxide 50; Drip off in 2 hours, continue insulation reaction 2～5 hours to reaction system oxirane value and no longer change, reaction finishes postcooling to room temperature; Filter, reclaim catalyzer, drip dilute sodium hydroxide aqueous solution in the filtrating; Regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back, behind the standing demix; Remove lower floor's water, behind the upper oil phase drying under reduced pressure, get epoxy aliphatic ester; Said catalyzer is S 2O 8 2-/ mesoporous Z rO 2Catalyzer, S 2O 8 2-/ mesoporous T iO 2Catalyzer, S 2O 8 2-/ mesoporous S nO 2Catalyzer and metal Schiff's base/cellular silica
Arbitrary.Also can adopt the direct epoxidation of natural plant grease to prepare the bio-based epoxy aliphatic ester.
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01～1:0.001 and catalyzer add in an amount of solvent, after stirring, add in the autoclave of acid and alkali-resistance, stir and are warming up to 60～140 ℃, feeding CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0～7.0MPa, keeps reaction pressure and temperature, reaction 6～24h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether.Said catalyzer is the arbitrary of pentanedioic acid zinc catalyst, pimelic acid zinc catalyst, Zinc dibenzoate catalyzer, diimine zinc catalyst, porphyrin chromium, Cobalt Porphyrin and SalenCr catalyzer; Said solvent is THF, N, dinethylformamide, N, arbitrary in N-DMSO 99.8MIN., the N-N-methyl-2-2-pyrrolidone N-.
Above-described solvent and catalyzer are all recyclable, reuse.And aforesaid method is equally applicable to behind the synthetic unsaturated fatty acid ester of the direct epoxidation of natural plant grease and CO 2Prepared in reaction biological poly carbonic ether.
The present invention is a kind of, and prepare the preferred version of method of biological poly carbonic ether with natural plant grease as shown in Figure 4; With the natural plant grease is raw material, separates through hydrolysis earlier, obtains highly purified unsaturated fatty acid ester; Again with formic acid prepared in reaction epoxy aliphatic ester, last and CO 2Polymerization reaction take place, preparation biological poly carbonic ether.The raw material natural green is renewable, and product is easy to separate, excellent property, and purity is high, but and solvent for use and all high efficiente callbacks of catalyzer in the reaction, reuse environmental friendliness.
Described bio-based epoxy aliphatic ester by the concrete steps that the direct epoxidation of natural plant grease obtains is: be after the ratio of 1 ~ 2:1 mixes natural plant grease and formic acid in the mol ratio of natural plant grease and formic acid, add the quality percentage that accounts for the natural plant grease consumption while stirring and be 0.5 ~ 5% epoxidation catalyst, mechanical stirring is warming up to 50 ~ 70 ℃ after evenly; It is 30 ~ 50% ydrogen peroxide 50 that constant speed drips the mass concentration account for natural plant grease consumption 30 ~ 60%; Drip off in 2 hours, continued insulation reaction 2 ~ 5 hours, reaction finishes postcooling to room temperature; Filter; Regulate filtrating pH value to 6.0～6.9, distilled water wash is used in the back, behind the standing demix; After getting the upper oil phase drying under reduced pressure, get the bio-based epoxy aliphatic ester.
With embodiment above-mentioned reaction process is described below.
Embodiment 1:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of tung oil and sodium hydroxide is 1:3, and methyl alcohol is slightly excessive; Add there-necked flask with methyl alcohol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 2h generally at 60 ℃ of following dropwise reaction 3h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with low-carbon alcohol by mass ratio 1:3, and in 0 ℃ of precooling and-20 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims methyl alcohol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 1% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous Z rO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 30% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 50% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 5 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 4.68;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and pentanedioic acid zinc catalyst add an amount of N, in the dinethylformamide; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 80 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 7.0MPa, keeps reaction pressure and temperature, reaction 24h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 82.3% with epoxy aliphatic ester, and number-average molecular weight is 21000, and MWD is 1.17.
Embodiment 2:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of coptis wood oil and sodium hydroxide is 1:1, and methyl alcohol is slightly excessive; Add there-necked flask with methyl alcohol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 5h generally at 70 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with methyl alcohol by mass ratio 1:5, and in 1 ℃ of precooling and-15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims methyl alcohol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 4:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous Z rO 2Catalyzer, mechanical stirring are warming up to 60 ℃ after evenly, and dripping 40% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 40% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 2 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 4.82;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.005 and pimelic acid zinc catalyst add an amount of N, in the N-dimethyl methyl sulfoxide; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 100 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 6.0MPa, keeps reaction pressure and temperature, reaction 18h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 80.7% with epoxy aliphatic ester, and number-average molecular weight is 18000, and MWD is 1.14.
Embodiment 3:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of VT 18 and sodium hydroxide is 1:5, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 2h generally at 80 ℃ of following dropwise reaction 1h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:4, and in 0 ℃ of precooling and-20 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 5:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 10% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous Z rO 2Catalyzer, mechanical stirring are warming up to 50 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 50% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 3 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.06;
The 3rd step; Synthesizing of biological poly carbonic ether: with mol ratio be: the epoxy aliphatic ester of 1:0.001 and Zinc dibenzoate catalyzer add in an amount of N-N-methyl-2-2-pyrrolidone N-, after stirring, add in the autoclave of acid and alkali-resistance; Stirring is warming up to 120 ℃, feeds CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 5.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 86.8% with epoxy aliphatic ester, and number-average molecular weight is 23000, and MWD is 1.10.
Embodiment 4:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of plam oil and sodium hydroxide is 1:3, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature generally at 80 ℃ of following dropwise reaction 2h, is incubated 1 h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:3, and in 0 ℃ of precooling and-18 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 60% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 2 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.58;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and diimine zinc catalyst add an amount of N, in the dinethylformamide; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 140 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 5.0MPa, keeps reaction pressure and temperature, reaction 6h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether.Productive rate is calculated as 88.3% with epoxy aliphatic ester, and number-average molecular weight is 22000, and MWD is 1.16.
Embodiment 5:
The first step, the hydrolysis of natural plant grease separates: smooth bark oil is 1:3 with the mol ratio of sodium hydroxide, and propyl alcohol is slightly excessive; Add there-necked flask with propyl alcohol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 1.5h generally at 80 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with low-carbon alcohol by mass ratio 1:3, and in 0 ℃ of precooling and-15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims propyl alcohol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous S nO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping the mass concentration that accounts for unsaturated fatty acid ester consumption 60% through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.32;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and porphyrin chrome catalysts add in an amount of tetrahydrofuran solvent, after stirring, add in the autoclave of acid and alkali-resistance, stir and are warming up to 60 ℃, feeding CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether.Productive rate is calculated as 76.0% with epoxy aliphatic ester, and number-average molecular weight is 16000, and MWD is 1.24.
Embodiment 6:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of Jatropha curcas oil and sodium hydroxide is 1:3, and Virahol is slightly excessive; Add there-necked flask with Virahol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature generally at 80 ℃ of following dropwise reaction 2h, is incubated 1 h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with Virahol by mass ratio 1:3, and in 0 ℃ of precooling and-15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims Virahol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid adding of 3:1 has churned mechanically there-necked flask, after the mixing; Add the quality percentage account for the unsaturated fatty acid ester consumption while stirring and be nickel Schiff's base/cellular silica catalyzer of 5%, mechanical stirring is warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50; Drip off in 2 hours, continued insulation reaction 4 hours, reaction finishes postcooling to room temperature; Filter, reclaim catalyzer, drip dilute sodium hydroxide aqueous solution in the filtrating; Regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back, behind the standing demix; Remove lower floor's water, behind the upper oil phase drying under reduced pressure, get epoxy aliphatic ester; Measure through hydrochloric acid-acetone method, oxirane value is 5.86;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and Cobalt Porphyrin catalyzer add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 120 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether.Productive rate is calculated as 84.0% with epoxy aliphatic ester, and number-average molecular weight is 20000, and MWD is 1.19.
Embodiment 7:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of rubber seed oil and sodium hydroxide is 1:3, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 1h generally at 80 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:3, and in 0 ℃ of precooling and--15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.34;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and SalenCr catalyzer add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 60 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 82.7% with epoxy aliphatic ester, and number-average molecular weight is 15000, and MWD is 1.30.
Embodiment 8:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of shinyleaf yellowhorn oil and sodium hydroxide is 1:3, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 1h generally at 80 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:3, and in 0 ℃ of precooling and--15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.52;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and SalenCr catalyzer add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 60 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 80.1% with epoxy aliphatic ester, and number-average molecular weight is 18000, and MWD is 1.14.
Embodiment 9:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of Camellia oil and sodium hydroxide is 1:3, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 1h generally at 80 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:3, and in 0 ℃ of precooling and--15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.86;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and SalenCr catalyzer add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 60 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 85.8% with epoxy aliphatic ester, and number-average molecular weight is 21000, and MWD is 1.13.
Embodiment 10:
The first step, the hydrolysis of natural plant grease separates: the mol ratio of Oleum Gossypii semen and sodium hydroxide is 1:3, and ethanol is slightly excessive; Add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed, and mechanical stirring is even; Reflux temperature is incubated 1h generally at 80 ℃ of following dropwise reaction 2h, and dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature; Standing demix under the room temperature, lower floor is the raw glycerine phase, recyclable extraction glycerine; The upper strata croude fatty acids of telling is mixed sealing with ethanol by mass ratio 1:3, and in 0 ℃ of precooling and--15 ℃ of each 2h of freezing, filter at low temperature gets clear filtrate; Filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, it is 5% S that adding while stirring accounts for the quality percentage of unsaturated fatty acid ester consumption 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.02;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and SalenCr catalyzer add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 60 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 3.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 85.1% with epoxy aliphatic ester, and number-average molecular weight is 22000, and MWD is 1.11.
Embodiment 11:
Present embodiment solvent for use and catalyzer are recovered solvent and catalyzer among the embodiment 4.
The first step, the hydrolysis of natural plant grease separates: the mol ratio of Jatropha curcas oil and sodium hydroxide is 1:3, and the ethanol of recovery is made solvent; Slightly excessive, add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed; Mechanical stirring is even, and reflux temperature generally at 80 ℃ of following dropwise reaction 2h, is incubated 1 h; Dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature, standing demix under the room temperature, and lower floor is the raw glycerine phase; Recyclable extraction glycerine mixes sealing with ethanol by mass ratio 1:3 with the upper strata croude fatty acids of telling, in 0 ℃ of precooling and-15 ℃ of each 2h of freezing; Filter at low temperature gets clear filtrate, and filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, adding while stirring accounts for the S that the quality percentage of unsaturated fatty acid ester consumption is 5% recovery 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 5.02;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the diimine zinc catalyst of the epoxy aliphatic ester of 1:0.01 and recovery adds an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 120 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 5.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 78.1% with epoxy aliphatic ester, and number-average molecular weight is 18000, and MWD is 1.16.
Embodiment 12:
Present embodiment solvent for use and catalyzer are recovered solvent and catalyzer among the embodiment 11.
The first step, the hydrolysis of natural plant grease separates: the mol ratio of Jatropha curcas oil and sodium hydroxide is 1:3, and the ethanol of recovery is made solvent; Slightly excessive, add there-necked flask with ethanol after NaOH is dissolved in zero(ppm) water, grease is added drop-wise to there-necked flask from the separating funnel constant speed; Mechanical stirring is even, and reflux temperature generally at 80 ℃ of following dropwise reaction 2h, is incubated 1 h; Dripping hydrochloric acid is regulated pH value to 3～4 behind the cool to room temperature, standing demix under the room temperature, and lower floor is the raw glycerine phase; Recyclable extraction glycerine mixes sealing with ethanol by mass ratio 1:3 with the upper strata croude fatty acids of telling, in 0 ℃ of precooling and-15 ℃ of each 2h of freezing; Filter at low temperature gets clear filtrate, and filter cake dissolving back underpressure distillation gets sfas.The filtrate decompression distillation gets unsaturated fatty acid ester, reclaims ethanol.
In second step, the epoxidation of unsaturated fatty acid ester: with mol ratio is that unsaturated fatty acid ester and the formic acid of 3:1 adds and has churned mechanically there-necked flask, and after the mixing, adding while stirring accounts for the S that the quality percentage of unsaturated fatty acid ester consumption is 5% recovery 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping 50% the mass concentration that accounts for the unsaturated fatty acid ester consumption through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get epoxy aliphatic ester, measure through hydrochloric acid-acetone method, oxirane value is 4.36;
In the 3rd step, biological poly carbonic ether synthetic: with mol ratio be: the diimine zinc catalyst of the epoxy aliphatic ester of 1:0.01 and recovery adds an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 120 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 5.0MPa, keeps reaction pressure and temperature, reaction 12h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 70.3% with epoxy aliphatic ester, and number-average molecular weight is 15000, and MWD is 1.21.
Embodiment 13:
Present embodiment does not separate natural plant grease through hydrolysis, direct epoxidation, obtain the epoxyfatty acid Witepsol W-S 55 after, with CO 2Prepared in reaction biological poly carbonic ether
The first step, the epoxidation of natural plant grease: with mol ratio is that natural plant grease and the formic acid of 1:1 adds and has churned mechanically there-necked flask, after the mixing, adds the quality percentage that accounts for the natural plant grease consumption while stirring and be 5% S 2O 8 2-/ mesoporous T iO 2Catalyzer, mechanical stirring are warming up to 70 ℃ after evenly, and dripping the mass concentration that accounts for natural plant grease consumption 50% through the tap funnel constant speed is 30% ydrogen peroxide 50, drips off in 2 hours; Continued insulation reaction 4 hours, reaction finishes postcooling to room temperature, filters, and reclaims catalyzer; Drip dilute sodium hydroxide aqueous solution in the filtrating, regulate pH value to 6.0～6.9, repeatedly wash with zero(ppm) water the back; Behind the standing demix, remove lower floor's water, behind the upper oil phase drying under reduced pressure; Get the epoxyfatty acid Witepsol W-S 55, measure through hydrochloric acid-acetone method, oxirane value is 5.82;
In second step, biological poly carbonic ether synthetic: with mol ratio be: the epoxy aliphatic ester of 1:0.01 and diimine zinc catalyst add an amount of N, in the dinethylformamide solvent; After stirring; Add in the autoclave of acid and alkali-resistance, stir and be warming up to 140 ℃, feed CO 2Gas is closed intake valve, opens air outlet valve, to drive the air in the reaction kettle away, behind the triplicate, feeds CO 2Gas to reacting kettle inner pressure reaches 5.0MPa, keeps reaction pressure and temperature, reaction 24h.After reaction finished, cooling reaction still temperature reduced reaction kettle pressure to normal pressure to room temperature, takes out reaction solution; After hot wash, static layering, catalyzer and solvent are reclaimed in the underpressure distillation of lower layer of water phase; Catalyzer repeatedly with after the hot wash oven dry, is waited to reuse, and solvent recuperation is waited to reuse.Residual solvent and moisture are removed in 120 ℃ of underpressure distillation of upper oil phase, get the biological poly carbonic ether, and productive rate is calculated as 70.4% with epoxy aliphatic ester, and number-average molecular weight is 11000, and MWD is 1.74.

Claims (9)

1. a biological poly carbonic ether is characterized in that, is raw material and CO with the bio-based epoxy aliphatic ester 2The gas polymerization obtains the biological poly carbonic ether, productive rate>=70%, and number-average molecular weight is 11000 ~ 30000, MWD is 1.10 ~ 1.74; Epoxidation obtains described bio-based epoxy aliphatic ester in order to be gone out behind the unsaturated fatty acid ester again by natural plant grease elder generation hydrolysis subzero fractionation, is perhaps obtained by the direct epoxidation of natural plant grease.
2. biological poly carbonic ether as claimed in claim 1 is characterized in that: described natural plant grease is arbitrary in tung oil, coptis wood oil, VT 18, plam oil, smooth bark oil, Jatropha curcas oil, rubber seed oil, shinyleaf yellowhorn oil, Camellia oil or the Oleum Gossypii semen.
3. method for preparing the described biological poly carbonic ether of claim 1; It is characterized in that; Mol ratio according to bio-based epoxy aliphatic ester and catalyzer is: the ratio of 1:0.01～1:0.005; Bio-based epoxy aliphatic ester, solvent and catalyzer are stirred, be warming up to 80～140 ℃, oxygen free condition feeds CO down 2Gas to 1.0～7.0MPa keeps reaction pressure and temperature, react to the reaction system oxirane value no longer to change, reaction solution with hot wash after, get the oil phase underpressure distillation, remove residual solvent, the biological poly carbonic ether.
4. the method for preparing the biological poly carbonic ether according to claim 2 is characterized in that, described bio-based epoxy aliphatic ester goes out behind the unsaturated fatty acid ester again by natural plant grease elder generation hydrolysis subzero fractionation that epoxidation obtains; Concrete steps are: the first step, and the hydrolysis subzero fractionation of natural plant grease: natural plant grease in molar ratio: sodium hydroxide is 1:3 ~ 1:5, the ratio that low-carbon alcohol is excessive; Natural plant grease, low-carbon alcohol and aqueous sodium hydroxide solution be blended under the reflux temperature react, after reaction finishes, conditioned reaction system pH to 3～4; Standing demix mixes sealing with low-carbon alcohol by mass ratio 1:3～5 with the supernatant liquid of telling, earlier at 0～1 ℃ of precooling 2h; The back is freezing 2h under-20～-15 ℃; Cross and filter clear filtrate, the clear filtrate underpressure distillation gets unsaturated fatty acid ester;
Second step; The epoxidation of unsaturated fatty acid ester: the mol ratio according to unsaturated fatty acid ester and formic acid is the ratio of 1～2:1; Unsaturated fatty acid ester, formic acid and epoxidation catalyst are mixed stirring be warming up to 50～70 ℃; The dropping mass concentration is 30～50% ydrogen peroxide 50, drips off in 2 hours, continues insulation reaction to reaction system oxirane value and no longer changes; The quality percentage that the epoxidation catalyst consumption accounts for the unsaturated fatty acid ester consumption is 0.5%～5%, and the ydrogen peroxide 50 consumption accounts for 30%～60% of unsaturated fatty acid ester consumption; After above-mentioned reaction finishes, filter, regulate filtrating pH value to 6.0～6.9, washing, behind the standing demix, get the upper oil phase drying under reduced pressure after, get the bio-based epoxy aliphatic ester.
5. the method for preparing the biological poly carbonic ether according to claim 4 is characterized in that: the described low-carbon alcohol of the first step is arbitrary in methyl alcohol, ethanol, propyl alcohol, the Virahol.
6. the method for preparing the biological poly carbonic ether according to claim 2 is characterized in that: described bio-based epoxy aliphatic ester is obtained by the direct epoxidation of natural plant grease, and concrete steps are: be after the ratio of 1 ~ 2:1 mixes natural plant grease and formic acid in the mol ratio of natural plant grease and formic acid; Add the quality percentage account for the natural plant grease consumption while stirring and be 0.5 ~ 5% epoxidation catalyst, mechanical stirring is warming up to 50 ~ 70 ℃ after evenly, and it is 30 ~ 50% ydrogen peroxide 50 that constant speed drips the mass concentration that accounts for natural plant grease consumption 30 ~ 60%; Drip off in 2 hours, continued insulation reaction 2 ~ 5 hours, reaction finishes postcooling to room temperature; Filter; Regulate filtrating pH value to 6.0～6.9, distilled water wash is used in the back, behind the standing demix; After getting the upper oil phase drying under reduced pressure, get the bio-based epoxy aliphatic ester.
7. according to claim 4 or the 6 described methods that prepare the biological poly carbonic ether, it is characterized in that: described epoxidation catalyst is S 2O 8 2-/ mesoporous Z rO 2Catalyzer, S 2O 8 2-/ mesoporous T iO 2Catalyzer, S 2O 8 2-/ mesoporous S nO 2Arbitrary in catalyzer or the nickel Schiff's base/cellular silica.
8. the method for preparing the biological poly carbonic ether according to claim 3 is characterized in that: described solvent is THF, N, dinethylformamide, N, arbitrary in N-DMSO 99.8MIN., the N-N-methyl-2-2-pyrrolidone N-.
9. the method for preparing the biological poly carbonic ether according to claim 3 is characterized in that: described catalyzer is the arbitrary of pentanedioic acid zinc catalyst, pimelic acid zinc catalyst, Zinc dibenzoate catalyzer, diimine zinc catalyst, porphyrin chromium, Cobalt Porphyrin and SalenCr catalyzer.
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