CN102453242A - Method for preparing oligofuran dioctyl phthalate ester by directly esterifying and polymerizing - Google Patents
Method for preparing oligofuran dioctyl phthalate ester by directly esterifying and polymerizing Download PDFInfo
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Abstract
The invention discloses a method for preparing oligofuran dioctyl phthalate ester by directly esterifying and polymerizing. The method is characterized by comprising the following steps of: under the action of a compound catalyst, undergoing esterification and polymerization reactions on 2,5-furan dioctyl phthalate and low-carbon diatomic alcohol serving as raw materials at the temperature of 130-280 DEG C under the pressure of 2-15 mmHg for 1.5-16 hours; removing excessive low-carbon diatomic alcohol and other impurities by using a vacuum distillation or azeotropic distillation method; and purifying a polymer product with a dissolving-precipitating technology to obtain a high-quality oligofuran dioctyl phthalate ester product. The method has the advantages of high product yield, easiness in separating the product and good application prospect.
Description
Technical field
The present invention relates to macromolecule polymer material and chemical field, particularly, relate to 2,5-furans dioctyl phthalate and the direct esterification under katalysis of low-carbon (LC) divalent alcohol, polymerization prepare high-quality method of gathering furans dicarboxylic acid esters macromolecular material.
Background technology
Synthesizing in petrochemical complex is synthetic of plastics, chemical fibre, polyester etc. occupies important status.The traditional preparation process method of these macromolecular materials mainly depends on fossil resources such as coal, oil and natural gas, after transforming through multistep, obtains organic polymer material monomer and polymeric articles.The reserves of fossil resource such as coal, oil and natural gas are limited, and non-renewable.In order to realize sustainable development, develop biomass resource reproducible, that reserves are abundant, the shortage with alternative or additional fossil resource has very important significance, and receives the extensive concern and the attention of domestic and international scientific circles and industry member.
Pure terephthalic acid (PTA) is the crucial monomer of large petrochemicals and engineering plastics.After terephthalic acid and the polymerization of low-carbon (LC) divalent alcohol, can obtain the polymerization product that polyethylene terephthalate (PET), PTT (PPT), polybutylene terephthalate (PBT) etc. have significant application value respectively.China's production capacity of PTA at present reaches more than 1,500 ten thousand tons, and demand is big.Study and explore new renewable raw material monomer, substitute the product of bulk chemical PTA, have great importance and prospect.
Biomass are organic carbon resources of the unique recyclable regenerative of nature, also are the important form of conversion of solar energy and storage.Glucide such as Mierocrystalline cellulose, semicellulose, glucose are one of most important biomass resources, recyclable regenerative, and stock number is big.With the glucide is raw material, waits the chemical conversion process through dehydration, can obtain important monomer and compounds such as 5 hydroxymethyl furfural, and this compound has become one of important hardware and software platform compound in the biorefinery.In the last few years,, carried out a large amount of research, (seen Science like J.A.Dumesic around the preparation and the preparation method of 5 hydroxymethyl furfural; 2006,312,1933-1937), Z.C.Zhang (sees Science; 2007,316,1597-1600), J.Y.Ying (sees Angew.Chem.Int.Ed.; 2008,47,9345-9348), R.T.Raines (sees J.Am.Chem.Soc.; 2009,131,1979-1985) wait the influence to preparation 5 hydroxymethyl furfural yield such as the biomass material studied different sources, catalyzer, solvent, reaction conditions.The 5 hydroxymethyl furfural selective oxidation transforms system 2, and the research of 5-furans dioctyl phthalate also has some reports, (sees Adv.Synth.Catal.2001 like V.V.Grushin; 343,102), K.D.Vorlop (sees Top.Catal.2000,13; 237), A.Corma (sees Chemsuschem 2009; 21138) and the research work of A.Riisager (seeing Chemsuschem 2009,2,672.) etc.The applicant has also carried out big quantity research to the preparation method of 5 hydroxymethyl furfural, selective oxidation conversion process etc., and has applied for that related patent U.S. Patent No. (sees one Chinese patent application number: 200810012159.X, 2009100012844.7,201010122864.2).
5 hydroxymethyl furfural and 2,5-furans dioctyl phthalate etc. all is a furan derivative, contains reactive groups such as furans heterocycle, hydroxyl, aldehyde radical or carboxyl, is easy to take place reactions such as polymerization, functional group's conversion.2,5-furans dioctyl phthalate has a lot of similaritys with terephthalic acid: the two all contains two carboxyls, has similar conjugated structure, the number of electrons on the conjugate ring is identical; As the surrogate of PTA, might be applied to the preparation of organic high molecular polymer material.With 2,5-furans dioctyl phthalate is that monomeric polymerization technique and product are actually rare but up to the present.
Research thinking of the present invention is to develop the novel method of a biomass material path of preparing organic polymer material; Replenish with part and substitute non-renewable fossil feedstock monomer, the macromolecular material that obtains having the important application prospect has important scientific meaning and using value.
Summary of the invention
The objective of the invention is; Develop a macromolecule polymeric material technology of preparing and a method that biomass resource is a raw material; The shortage of alleviating, substituting, replenish fossil resource for the macromolecular material of special construction and purposes synthesizes, provides the new technology and the novel method of Sustainable development.Specifically; Exactly with glucide through the dehydration and oxidation obtain 2,5-furans dioctyl phthalate is a monomer, under catalyst action; Through with the purification and the sepn process of esterification, polyreaction and the product of low-carbon (LC) divalent alcohol; Prepare the high-quality furans dicarboxylic acid esters product that gathers, and the structure and the performance of product are tested, for application provides reference and foundation.
According to route provided by the invention, one of esterification and monomer polymerized raw material are 2,5-furans dioctyl phthalate, and these monomers can be through the dehydration of biomass glucide and the acquisition of oxidising process; Another monomer is the low-carbon (LC) divalent alcohol, like 1,1, and 2-Ucar 35,1, ammediol or 1,4-butyleneglycol; These low-carbon (LC) divalent alcohol also can be made (see one Chinese patent application number: 200610165881.8,200710012574.0,200810011993.7,200910187393.0 etc.) by the biomass material catalyzed conversion.Therefore; Raw material monomer with these biomass sources adopts catalysis process, with 2; 5-furans diacid and low-carbon (LC) diol reaction; Through the steps such as purifies and separates of direct esterification reaction, polyreaction, intermediate and product, obtain high-quality technology and the route that gathers furans dicarboxylic acid esters base polymer novel material, be a new technology path that is different from and does not rely on fossil resources such as oil fully.
According to method provided by the invention; In order to improve reaction efficiency, reduce the loss and the consumption of separating step, adopt the strategy of two step such as direct esterification, polymerization process one pot reaction; Make 2, the esterification and the polyreaction of 5-furans dioctyl phthalate and low-carbon (LC) divalent alcohol are carried out in same reactor drum.Under catalyst action, make 2 earlier, 5-furans diacid and the direct esterification of low-carbon (LC) divalent alcohol generate 2; 5-furans dioctyl phthalate diol ester; Intermediary direct esterification product does not need to separate, and unreacted excessive low-carbon (LC) divalent alcohol is removed in underpressure distillation, under the rough vacuum condition, carries out polyreaction.The present invention has adopted and can realize direct esterification, polymeric dual-function catalyst simultaneously, comprises Sb
2O
3, Zn (OAc)
2, ZnCl
2, Ca (OAc)
2, PbO, Ti (n-OC
4H
9)
4, Ti (i-OC
4H
9)
4, SnCl
2Deng in the compound one or more.
Present known preparation gathers one of method of furans dicarboxylic acid esters macromolecular material, is to adopt 2, and 5-furans dioctyl phthalate dimethyl ester is the ester exchange method of raw material; Promptly under lime acetate and weisspiessglanz katalysis,, after the 6-pinakon carries out transesterify, obtain 2 with 1, and 5-furans dioctyl phthalate two pinakon esters (see J.A.Mooreand J.E.Kelly, Macromolecules, 1978,11,568-573).Compare with this method, method provided by the invention is except the raw material difference, and the method for employing is 2,5-furans dioctyl phthalate direct esterification method, rather than the method for transesterify.Method of the present invention has reduced the transesterify process, and step is more succinct and efficient.
The research report that adopts protonic acid catalysis direct esterification and transesterify is also arranged recently, and this method is with 2,5-furans dioctyl phthalate, 2; 5-furans dioctyl phthalate dimethyl ester is a raw material, respectively with excessive 1,1; Ammediol reaction, obtain 2,5-furans dioctyl phthalate binaryglycol ester (or furans diacid dipropylene glycol ester) intermediates through separate purify after; Repolymerization obtains gathering the furans dicarboxylic acid esters and (sees A.Gandini, et al, J.Polym.Sci.Pol.Chem. under the weisspiessglanz katalysis; 2009,47,295; J.Mater.Chem., 2009,19,8656.).Compare with this method, method provided by the invention is not used bronsted acid catalyst, can realize direct esterification and polyreaction simultaneously, has avoided spinoffs such as protonic acid corrosion and pollution; The intermediate product of esterification need not separate and promptly carries out polymerization in addition, though technical difficulty increases, the material and the power loss of sepn process also have vital role for pollution abatement in the middle of can significantly reducing.
In order to improve reaction efficiency, reduce side reaction and take place, the invention provides a kind of under nitrogen protection 2, the method for 5-furans dioctyl phthalate and low-carbon (LC) dibasic alcohol ester.Adopt this nitrogen protection method, can reduce the side reactions such as oxidation that cause because of inclusion of air and take place, avoid other nondirectional polymerization processes, improve the yield of esterification.2, the esterification optimized conditions of 5-furans dioctyl phthalate and low-carbon (LC) divalent alcohol is: nitrogen protection, temperature of reaction 150-170 ℃, the reaction times is 4-6h.
According to the present invention,, need carry out purifying to the esterification intermediate product for physics, the chemical property that improves polymerization process efficient and polymkeric substance; Promptly remove low-carbon (LC) divalent alcohol and other impurity that esterification does not take place, these impurity are very big for the quality influence of polymerization process and polymerization product.Though the separation method through complicacy also can obtain highly purified esterification intermediate product, route is very long, and raw material, energy expenditure are very big, causes cost to increase.The present invention has designed the method that United Technologies such as the esterification intermediate product does not separate, the distillation of original position vacuum decompression, azeotropic solvent azeotropic are carried out purifying.This method is not that the method that title product shifts out is carried out separation and purification, but the method that impurity removal shifts out is made the intermediate product purifying, with flow process in the middle of reducing, reduces raw material and energy expenditure, improves transformation efficiency, and reduction equipment drops into and cost.
According to the present invention, the impurity that the esterification intermediate product needs purifying to remove mainly is: the low-carbon (LC) divalent alcohol raw material of esterification does not take place in (1); (2) by product that generates in higher impurity of other boiling points or the esterification process.The boiling point of these impurity or by product is very high; If at high temperature straight run distillation removes and can cause a large amount of side reactions to take place, influence the yield and the quality of polymerization product.The invention provides a kind of under vacuum, component distillation removes the method for impurity, this method is operated under vacuum condition, can reduce the boiling point of low-carbon (LC) divalent alcohol and other impurity, improves the effect that evaporation removes.The working pressure of selecting is 2-15mmHg, and temperature is 190-280 ℃, and the time is 0.5-8h.Optimum pressure is 2-5mmHg, and optimum temps is 200-240 ℃, and Best Times is 2-4h.
According to the present invention, in order to strengthen the effect of impurity removal, in reaction system, add can with remove the azeotropic solvent that impurity forms azeotrope, not only can more effectively reduce boiling point, and can remove impurity more efficiently.The solvent that adds carries impurity and breaks away from reaction system, so that the esterification products purifying through component distillation.Requirement to azeotropic solvent itself is an inertia simultaneously, under azeotropic conditions, do not react with impurity, and water insoluble.Therefore, in the distillment that contains azeotropic solvent and impurity, add entry after, through simple standing demix, these azeotropic solvents are separated and recycle.Azeotropic solvent comprises: toluene, o-Xylol, m-xylene, p-Xylol, biphenyl, chlorobenzene, 1,2-dichlorobenzene, 1, one or more in the compounds such as 4-dichlorobenzene.
According to the present invention, the polymkeric substance that generates is carried out purifying, also be the key link with performance of improving the quality of products.The invention provides a kind of dissolving-sedimentary method; Realized the efficiently purifying of polymerisate.According to the method, the monomer of polymkeric substance is oxygen containing polar material; Therefore, polymkeric substance might be dissolved in intensive polar solvent, and in weak polar solvent, does not dissolve.Through dissolving-intermediate processing, can make those not have the impurity high efficiency separation of this specific character.Adopt trifluoroacetic acid intensive polar solvent dissolve polymer, be added drop-wise to then in the weak polar solvent methyl alcohol and precipitate,, obtain high-quality furans two acid esters that gather through spinning and washing.
According to method provided by the invention; For the impurity checking esterification, original position under the nitrogen protection not separate azeotropic under esterification intermediate product, the vacuum to remove esterification products, dissolving-precipitate and separate polymkeric substance etc. the effect of key element; The present invention tests the physicochemical property of final polymkeric substance, comprising: measure proton nmr spectra and (use
1H NMR representes), carbon-13 nmr spectra (uses
13C NMR representes), to confirm and to check the structure of polymkeric substance.Adopt technology such as heat analysiss-calorimetric, measured the fusing point (representing), 5% thermal weight loss temperature (rate of weight loss reaches 5% o'clock temperature in the temperature-rise period, representes with Td), second-order transition temperature (representing) of polymkeric substance etc., to check polymer thermostable property with Tg with Tm.The polymerization degree (representing) and elementary composition (the quality percentage composition with C, H, O is represented) of polymkeric substance etc. have been measured with DPn.
The present invention also has following characteristics:
System can highly selective, high conversion catalysis 2, and 5-furans diacid and glycol prepare the high-quality furans dicarboxylic acid esters that gathers, and the product separation yield is high.
13C NMR shows that polyester is a chain structure, does not have ring texture to exist.
1H NMR show polyester have the very high polymerization degree (DPn, 200-400).TG/DSC shows that such polyester macromolecule material of synthetic has good thermostability.
Embodiment
With specific embodiments the present invention is detailed below, but the present invention implements to be not limited to these embodiment:
Embodiment 1: with 10mmol 2, and 5-furans dioctyl phthalate, 20mmol 1,0.1mmolPbO join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 140 ℃; Under this temperature, react 4h.Excessive terepthaloyl moietie and other impurity are removed in distillation under reduced pressure then.Be warming up to 230 ℃, regulate vacuum tightness, continue reaction 3h to 5mmHg.Add the 2g o-Xylol at last, continue reaction 1h under these conditions.Be cooled to room temperature, add the dissolving of 10g trifluoroacetic acid, the trifluoroacetic acid polymers soln is added drop-wise in the methyl alcohol of 60ml precipitates then; Through spinning; Decant is removed supernatant liquid, and the polymer poly furans dioctyl phthalate second diester that obtains is an Off-white solid, at 50 ℃ of following vacuum-drying 12h.According to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, the molar yield 95% of this polymkeric substance.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 4.77 (s, 2H ,-O-CH
2-), 7.42 (s, 1H, furan-H).
13C?NMR(TFA-d
1，ppm)：64.8(-O-CH
2-)，121.2(C
3/C
4)，147.2(C
2/C
5)，161.1(C＝O)。Other physicochemical property are seen table 1.
Table 1: embodiment 1 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate second diester
Embodiment 2: with 10mmol 2, and 5-furans dioctyl phthalate, 11mmol 1, ammediol, 0.03mmol ZnCl
2Join in the 50mL round-bottomed flask, under nitrogen protection, be heated to 160 ℃, reaction 5h; Excessive Ucar 35 is removed in distillation under reduced pressure then, is warming up to 210 ℃, regulates vacuum tightness to 3mmHg; Continue reaction 2.5h, add 4g biphenyl at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 5g trifluoroacetic acid, its trifluoroacetic acid solution is added drop-wise to carries out precipitate and separate in the 60ml methyl alcohol then, centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate propylene diester is Off-white solid, 50 ℃ of vacuum-drying 12h.According to monomer 2, the charging capacity of 5-furans diacid is calculated, and the molar yield of this polymkeric substance is 96%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 2.05 (s, 2H ,-O-CH
2-CH
2-), 4.58 (s, 2H ,-O-CH
2-CH
2), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 27.4 (O-CH
2-CH
2-), 68.8 (O-CH
2-CH
2-), 122.7 (C
3/ C
4), 149.1 (C
2/ C
5), 162.8 (C=O).Other physicochemical property are seen table 2.
Table 2: embodiment 2 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate propylene diester
Embodiment 3: with 10mmol 2, and 5-furans dioctyl phthalate, 30mmol 1,4-butyleneglycol, 0.08mmolCa (OAc)
2Join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 180 ℃, reaction 6h.Excessive butyleneglycol is removed in distillation under reduced pressure then.Be warming up to 200 ℃, regulate vacuum tightness, continue reaction 3.5h to 4mmHg.Add the 5g chlorobenzene at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 15g trifluoroacetic acid, its trifluoroacetic acid solution is added drop-wise in the 60ml methyl alcohol precipitates then, spinning, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate fourth diester is Off-white solid.50 ℃ of vacuum-drying 12h.According to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 92%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 2.08 (s, 2H ,-O-CH
2-CH
2-), 4.61 (s, 2H ,-O-CH
2-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 26.8 (O-CH
2-CH
2-), 69.2 (O-CH
2-CH
2-), 122.4 (C
3/ C
4), 149.0 (C
2/ C
5), 163.5 (C=O).Other physicochemical property are seen table 3.
Table 3: embodiment 3 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate fourth diester
Embodiment 4: with 10mmol 2, and 5-furans diacid, 450mmol 1,4-butyleneglycol, 0.08mmolZn (OAc)
2Join in the 50mL round-bottomed flask, under nitrogen protection, be heated to 130 ℃, reaction 1h, excessive butyleneglycol is removed in distillation under reduced pressure then; Be warming up to 200 ℃, regulate vacuum tightness, continue reaction 1h to 13mmHg; Add 18g 1 at last, the 2-dichlorobenzene continues to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 20g trifluoroacetic acid, its trifluoroacetic acid solution is added drop-wise to carries out precipitate and separate in the 60ml methyl alcohol then, centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate fourth diester is Off-white solid, 50 ℃ of vacuum-drying 12h.According to monomer 2, the charging capacity of 5-furans diacid is calculated, and the molar yield of this polymkeric substance is 94%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 2.08 (s, 2H ,-O-CH
2-CH
2-), 4.61 (s, 2H ,-O-CH
2-CH
2-), 7.42 (s, 1H, furan-H).
13C?NMR(TFA-d
1，ppm)：26.8(-O-CH
2-CH
2-)，69.2(-O-CH
2-CH
2-)，122.4(C
3/C
4)，149.0(C
2/C
5)，163.5(C＝O)。Other physicochemical property are seen table 4.
Table 4: embodiment 4 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate fourth diester
Embodiment 5: with 10mmol 2, and 5-furans dioctyl phthalate, 50mmol 1,2-Ucar 35,0.2mmol Sb
2O
3Join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 170 ℃, reaction 8h.Excessive Ucar 35 is removed in distillation under reduced pressure then.Be warming up to 240 ℃, regulate vacuum tightness, continue reaction 1.5h to 10mmHg.Add the 8g m-xylene at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 3g trifluoroacetic acid.Then its trifluoroacetic acid solution is added drop-wise to and carries out precipitate and separate in the 60ml methyl alcohol, centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate propylene diester is Off-white solid.50 ℃ of vacuum-drying 12h, according to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 96%.Nmr spectrum is measured the result and attribution analysis is:
1HNMR (TFA-d
1, ppm): 2.05 (s, 2H ,-O-CH
2-CH
2-), 4.58 (s, 2H ,-O-CH
2-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 27.4 (O-CH
2-CH
2-), 68.8 (O-CH
2-CH
2-), 122.7 (C
3/ C
4), 149.1 (C
2/ C
5), 162.8 (C=O).Other physicochemical property are seen table 5.
Table 5: embodiment 5 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate propylene diester
Embodiment 6: with 10mmol 2, and 5-furans dioctyl phthalate, 25mmol 1,0.2mmolTi (i-OC
4H
9)
4Join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 130 ℃, reaction 6h.Excessive terepthaloyl moietie is removed in distillation under reduced pressure then.Be warming up to 280 ℃, regulate vacuum tightness, continue reaction 4h to 2mmHg.Add 10g oil of mirbane at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 28g trifluoroacetic acid.Then its trifluoroacetic acid solution is added drop-wise to and carries out precipitate and separate in the 60ml methyl alcohol, centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate second diester is Off-white solid.50 ℃ of vacuum-drying 12h, according to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 98%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 4.77 (s, 2H ,-O-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 64.8 (O-CH
2-), 121.2 (C
3/ C
4), 147.2 (C
2/ C
5), 161.1 (C=O).Other physicochemical property are seen table 6.
Table 6: embodiment 6 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate second diester
Embodiment 7: with 10mmol 2, and 5-furans dioctyl phthalate, 15mmol1,2-terepthaloyl moietie, 0.05mmol ZnCl
2, 0.05mmol PbO joins in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 130 ℃, reaction 2h.Excessive terepthaloyl moietie is removed in distillation under reduced pressure then.Be warming up to 280 ℃, regulate vacuum tightness, continue reaction 1h to 15mmHg.Add 10g toluene at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 20g trifluoroacetic acid.Then its trifluoroacetic acid solution is added drop-wise to and carries out precipitate and separate in the 60ml methyl alcohol, centrifugal, decant goes out supernatant liquid.Obtaining polymer poly furans dioctyl phthalate second diester is Off-white solid.50 ℃ of vacuum-drying 12h, according to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 98%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 4.77 (s, 2H ,-O-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 64.8 (O-CH
2-), 121.2 (C
3/ C
4), 147.2 (C
2/ C
5), 161.1 (C=O).Other physicochemical property are seen table 7.
Table 7: embodiment 7 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate second diester
Embodiment 8: with 10mmol 2, and 5-furans dioctyl phthalate, 26mmol1, ammediol, 0.2mmol Sb
2O
3Join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 140 ℃, reaction 7h.Excessive Ucar 35 is removed in distillation under reduced pressure then.Be warming up to 190 ℃, regulate vacuum tightness, continue reaction 4h to 13mmHg.Add the 12g chlorobenzene at last, continue to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 15g trifluoroacetic acid, its trifluoroacetic acid solution is added drop-wise to carries out precipitate and separate in the 60ml methyl alcohol then.Centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate propylene diester is Off-white solid.50 ℃ of vacuum-drying 12h, according to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 86%.Nmr spectrum is measured the result and attribution analysis is:
1HNMR (TFA-d
1, ppm): 2.05 (s, 2H ,-O-CH
2-CH
2-), 4.58 (s, 2H ,-O-CH
2-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 27.4 (O-CH
2-CH
2-), 68.8 (O-CH
2-CH
2-), 122.7 (C
3/ C
4), 149.1 (C
2/ C
5), 162.8 (C=O).Other physicochemical property are measured the result and are seen table 8.
Table 8: embodiment 8 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate second diester
Embodiment 9: with 10mmol 2, and 5-furans dioctyl phthalate, 50mmol 1,4-butyleneglycol, 0.08mmolTi (n-OC
4H
9)
4, 0.2mmol SnCl
2Join in the 50mL round-bottomed flask.Under nitrogen protection, be heated to 170 ℃, reaction 6h.Then under reduced pressure distillation remove excessive 1, the 4-butyleneglycol.Be warming up to 250 ℃, regulate vacuum tightness, continue reaction 8h to 8mmHg.Add 15g 1 at last, the 2-dichlorobenzene continues to react under these conditions 1h.Be cooled to room temperature, add the dissolving of 5g trifluoroacetic acid.Then its trifluoroacetic acid solution is added drop-wise to and carries out precipitate and separate in the 60ml methyl alcohol.Centrifugal, decant goes out supernatant liquid, and obtaining polymer poly furans dioctyl phthalate fourth diester is Off-white solid, 50 ℃ of vacuum-drying 12h, and according to monomer 2, the charging capacity of 5-furans dioctyl phthalate is calculated, and the molar yield of this polymkeric substance is 94%.Nmr spectrum is measured the result and attribution analysis is:
1H NMR (TFA-d
1, ppm): 2.08 (s, 2H ,-O-CH
2-CH
2-), 4.61 (s, 2H ,-O-CH
2-CH
2-), 7.42 (s, 1H, furan-H);
13C NMR (TFA-d
1, ppm): 26.8 (O-CH
2-CH
2-), 69.2 (O-CH
2-CH
2-), 122.4 (C
3/ C
4), 149.0 (C
2/ C
5), 63.5 (C=O).Other physicochemical property are measured the result and are seen table 9.
Table 9: embodiment 9 obtains gathering the physicochemical property mensuration result of furans dioctyl phthalate fourth diester
The present invention has developed a macromolecule polymeric material technology of preparing and a method that biomass resource is a raw material.Under catalyst action, through 2, the esterification of 5-furans dioctyl phthalate and low-carbon (LC) divalent alcohol, polymerization, product separation purification process, efficient, high-quality preparing gathered the furans dicarboxylic acid esters.Change low-carbon (LC) divalent alcohol monomer and polymerizing condition, fusing point, second-order transition temperature and the polymerization degree that can telomerized polymer.Excellent product performance.Be to alleviate and substitute the dependence for petroleum resources, the bio-based macromolecular material of synthetic special construction and purposes provides the new technology and the novel method of Sustainable development, has great importance and is worth.
Claims (6)
1. a direct esterification polymerization prepares the method for gathering the furans dicarboxylic acid esters, and it is characterized in that: with 2,5-furans dioctyl phthalate and low-carbon (LC) divalent alcohol are raw material; Under catalyst action; 2,5-furans dioctyl phthalate and low-carbon (LC) diol reaction are through direct esterification, polyreaction; Through purifies and separates, obtain the high-quality furans dicarboxylic acid esters that gathers.
2. method according to claim 1 is characterized in that: the low-carbon (LC) divalent alcohol in the reaction raw materials is a 1,1, ammediol or 1,4-butyleneglycol;
The catalyzer that uses is Sb
2O
3, Zn (OAc)
2, ZnCl
2, Ca (OAc)
2, PbO, Ti (n-OC
4H
9)
4, Ti (i-OC
4H
9)
4, SnCl
2In one or more plural components, catalyst levels is 2, the 0.2-3.0mol% of 5-furans dioctyl phthalate amount.
3. method according to claim 1 is characterized in that: 2, and the esterification of 5-furans dioctyl phthalate and low-carbon (LC) divalent alcohol and polyreaction are in same reactor drum, to carry out; Esterification is carried out under nitrogen protection, and temperature is 130-180 ℃, and the time is 1-8h;
Polyreaction is in same reactor drum, to carry out under the low vacuum, and reaction pressure is 2-15mmHg, and temperature is 190-280 ℃, and the time is 0.5-8h.
4. method according to claim 1 is characterized in that: the esterification optimum temps is 150-170 ℃, and Best Times is 4-6h;
Polyreaction optimum response pressure is 2-5mmHg, and optimum temps is 200-240 ℃, and Best Times is 2-4h.
5. method according to claim 1 is characterized in that: low-carbon (LC) divalent alcohol and 2, the mol ratio 1.1-5 of the consumption of 5-furans dioctyl phthalate: 1.
6. method according to claim 1; It is characterized in that: the method for purifying and separating of polymerisate; Be to add 1-20 doubly 2; Toluene, o-Xylol, m-xylene, biphenyl, the chlorobenzene or 1 of 5-furans dioctyl phthalate quality, one or more in the azeotropic solvent that the 2-dichlorobenzene can be recycled remove low-carbon (LC) divalent alcohol and other impurity through azeotropic; With 1-20 doubly 2, the trifluoroacetic acid dissolving of 5-furans dioctyl phthalate quality is added drop-wise to and makes polymer precipitation in the methyl alcohol then, through centrifugal and washing, obtains the high-quality furans dicarboxylic acid esters that gathers.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075141A (en) * | 1992-01-14 | 1993-08-11 | 拜尔公司 | 1,4-dihydropyridine-3, the preparation of 5-dicarboxylic acid esters and purposes |
-
2010
- 2010-10-27 CN CN 201010522893 patent/CN102453242B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075141A (en) * | 1992-01-14 | 1993-08-11 | 拜尔公司 | 1,4-dihydropyridine-3, the preparation of 5-dicarboxylic acid esters and purposes |
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