CN115785414A - Polyfurandicarboxylic acid-carbonic acid-butanediol ester and preparation method thereof - Google Patents
Polyfurandicarboxylic acid-carbonic acid-butanediol ester and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 49
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 22
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- -1 diethyl titanate Chemical compound 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- AIWZOHBYSFSQGV-LNKPDPKZSA-M sodium;(z)-4-oxopent-2-en-2-olate Chemical compound [Na+].C\C([O-])=C\C(C)=O AIWZOHBYSFSQGV-LNKPDPKZSA-M 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 19
- 239000000155 melt Substances 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 10
- 239000003208 petroleum Substances 0.000 abstract description 7
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- 229920001634 Copolyester Polymers 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 17
- 238000005469 granulation Methods 0.000 description 14
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- 125000003118 aryl group Chemical group 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 102100021669 Stromal cell-derived factor 1 Human genes 0.000 description 1
- 101710088580 Stromal cell-derived factor 1 Proteins 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
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- 229920000229 biodegradable polyester Polymers 0.000 description 1
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- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a novel composite catalyst and a method for preparing biomass polyfurandicarboxylic acid-butylene carbonate (PBCF) by using the composite catalyst. The composite catalyst for preparing PBCF is prepared by reacting alkali metal, titanate, phosphate and tetraethoxysilane at a certain temperature by taking ethanol as a solvent; the composite catalyst, 2, 5-furandicarboxylic acid or ester thereof, dimethyl carbonate and butanediol are put into a reaction kettle together to prepare PBCF. The method can effectively improve the esterification rate, reduce thermal degradation, improve the polymerization rate and greatly shorten the production period. The prepared product has the intrinsic viscosity of 1.2-2.0 dL/g, the melt index of 3-20 g/10min, the yield of more than 95 percent and the preparation time of 2-6 h. The bio-based PBCF has excellent comprehensive performance, realizes partial marketization substitution of petroleum-based polyester, and can effectively reduce the use of petroleum resources.
Description
Technical Field
The invention belongs to the technical field of synthesis of biodegradable high polymer materials, and particularly relates to a novel composite catalyst for synthesizing polyfurandicarboxylic acid-carbonic acid-butanediol ester (PBCF) and a preparation method thereof.
Background
With the development of fossil energy and petrochemical industries, the emission of greenhouse gases by carbon is continuously increased, so that the global climate is warmed, and people are greatly affected by energy and environmental problems. Therefore, bio-based chemical monomer raw materials capable of replacing the current petroleum are searched globally to realize sustainable, green and environment-friendly development of macromolecules and related fine chemical industries. In 2004, the U.S. department of energy has sought 30 corresponding important bio-based platform compounds for over 300 petroleum-based products, and further screened twelve bio-based platform compounds that are currently considered to be most likely to realize petroleum-based replacement. 2, 5-furandicarboxylic acid (2, 5-FDCA) is the only bio-based platform compound with an aromatic ring plane and a rigid structure in twelve platform compounds, is mainly used for replacing benzene ring series in eight basic platform compounds of petroleum base, particularly Terephthalic Acid (PTA), and has extremely similar physicochemical properties. Both research institutions and large-scale companies at home and abroad increase the research strength of FDCA, the technology is gradually mature, the cost is gradually reduced, and large-scale industrial production can be quickly realized.
With the vigorous development of biodegradable polyester poly (butylene adipate-co-terephthalate) (PBAT) and poly (butylene succinate-co-terephthalate) (PBST), the copolymerization of aromatic polyester and aliphatic polyester to optimize the degradation performance thereof has become a consensus in the whole industry. At present, aromatic-aliphatic degradable polyesters such as PBAT, PBST and the like are mostly used for disposable plastic products, and the pollution of non-degradable polyesters to the ecological environment is reduced. Meanwhile, a large amount of degradable polyester is discarded after being used once for degradation, so that huge petroleum resources are wasted. Therefore, the use of bio-based raw materials instead of terephthalic acid (PTA) for the production of degradable polyesters will effectively reduce the use of petroleum, an irreproducible resource. The preparation and physicochemical properties of PBSF and PBAF were analyzed in detail in the literature Biomaterials,2012,13. The documents J.appl.Polym.Sci.,2017,134 (15): 44674 and Polym.Degrad.Stabil, 2017, 146.
Compared with aromatic-aliphatic copolyesters such as PBAT and PBST, the poly (butylene terephthalate-co-butylene carbonate) (PBCT) has shorter aliphatic carbon chain length in the main chain repeating unit structure, so the mechanical strength of the poly (butylene terephthalate-co-butylene carbonate) (PBST) is better than that of the PBAT and PBST (CN 103265689A). In addition, in the PBCT main chain repeating unit, DMC can be produced by carbonylation of carbon dioxide and methanol, large-scale production is realized, so the biomass content of DMC is superior to PBAT and PBST, if PTA in the PBCT main chain structure is also replaced by FDCA, the preparation of PBCF of biomass aromatic-aliphatic copolyester is realized, and because furan rings do not have plane overturning capacity, the barrier and weather resistance of the biomass aromatic-aliphatic copolyester are further improved, and the application of the biomass aromatic-aliphatic copolyester in the fields of agricultural mulching films, disposable products and the like is expanded. PBCF is used as a biomass degradable polyester with excellent comprehensive performance, and the production process has the technical problems of complex production steps, long polycondensation time, low product yield, high production energy consumption and the like.
Disclosure of Invention
The invention aims to provide a preparation method of polyfurandicarboxylic acid-butylene carbonate, and provides a high-activity composite catalyst aiming at the problems of complex production steps, long polycondensation time, low product yield and high production energy consumption in the synthesis process of PBCF copolyester, and the composite catalyst is used for preparing PBCF copolyester. The novel composite catalyst is mainly prepared from alkali metal, titanate, phosphate and ethyl orthosilicate, and the synthesis process of PBCF is optimized by a one-pot method. The novel composite catalyst has high catalytic efficiency, can greatly shorten the production period of PBCF, and can fundamentally solve the problems of high energy consumption caused by the long production period of polyester and raw material loss caused by stepwise esterification.
The invention discloses a method for preparing polyfurandicarboxylic acid-butylene carbonate by a one-pot method, which comprises the steps of adding 2, 5-furandicarboxylic acid or dimethyl ester thereof, dimethyl carbonate and 1, 4-butanediol into a reaction kettle together according to a proportion, and preparing biomass aromatic-aliphatic PBCF copolyester by esterification reaction, pre-polycondensation reaction and final polycondensation reaction under the action of a composite catalyst; the dosage of the composite catalyst is 0.01 to 0.5 percent of the total weight of the 2, 5-furandicarboxylic acid or dimethyl ester thereof, the dimethyl carbonate and the 1, 4-butanediol in the reaction system;
the preparation raw materials of the composite catalyst comprise alkali metal, titanate, phosphate and tetraethoxysilane; the molar ratio of the alkali metal to the titanate is 1-1; the molar ratio of the alkali metal to the phosphate is 1 to 1; the molar ratio of the alkali metal to the ethyl orthosilicate is 1.
Further, the composite catalyst is prepared by adopting the following method:
firstly, adding alkali metal, titanate, phosphate and ethyl orthosilicate into absolute ethyl alcohol, and reacting for no more than 4 hours at the temperature of 30-80 ℃; and then adding deionized water, continuing to react for 2-3 h, fully cooling the reactant to room temperature, filtering, and drying in vacuum to obtain a white solid, namely the composite catalyst.
Further, the molar ratio of the dimethyl carbonate to the 2, 5-furandicarboxylic acid or the dimethyl ester thereof is 1; the ratio of the molar weight of the ester group or the sum of the molar weight of the ester group and the molar weight of the carboxyl group to the molar weight of the hydroxyl group in the reaction system in the reaction kettle is 1-2.5.
Further, the alkali metal is at least one of sodium methoxide, sodium ethoxide, sodium hydroxide and sodium acetylacetonate; the titanate is at least one of diethyl titanate, tetra-tert-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate; the phosphate is at least one of triphenyl phosphite, triphenyl phosphate and triethyl phosphate.
Further, the molar ratio of the alkali metal to the titanate is 1 to 1; the molar ratio of the alkali metal to the phosphate is 1 to 1; the molar ratio of the alkali metal to the tetraethoxysilane is 1; the molar ratio of the alkali metal to the absolute ethyl alcohol is 1.
Further, during the esterification reaction, under the protection of inert gas, 2, 5-furandicarboxylic acid or dimethyl ester thereof, dimethyl carbonate, 1, 4-butanediol and a composite catalyst are added into a reaction kettle together, and the esterification reaction is carried out under the action of the composite catalyst, wherein the esterification reaction temperature is 110-180 ℃, and the reaction time is 2-8 h.
Further, slowly heating to 180-200 ℃ for pre-polycondensation reaction, wherein the pre-polycondensation reaction lasts for not less than 1h.
Further, the final polycondensation temperature is 200-260 ℃, the reaction time is not less than 1h, and the biomass polyfuran dicarboxylic acid-carbonic acid-butanediol ester is obtained after the final polycondensation reaction is finished.
The sum of the time of the pre-polycondensation reaction and the time of the final polycondensation reaction is 2 to 6 hours.
Further, the vacuum degree in the reaction kettle is gradually improved in the pre-polycondensation reaction, and when the vacuum degree is 500Pa, the pressure is maintained for not less than 1h.
Further, the pressure of the vacuum environment in the reaction kettle of the final polycondensation reaction is less than 200Pa.
Further, the method also comprises the following steps of water-cooling granulation: and (3) directly feeding the prepared PBCF into a granulator for granulation after water cooling and drafting, and drying the obtained master batch in a vacuum oven at 25 ℃ for 24 hours to obtain kilogram-grade PBCF copolyester.
Further, the air inside the reaction vessel was evacuated by an inert gas substitution method prior to the esterification.
In a second aspect, the invention discloses a polyfurandicarboxylic acid-butylene carbonate prepared by the method, wherein the chemical structural formula of the polyfurandicarboxylic acid-butylene carbonate is as follows:
wherein n is the number of repeating units of the polybutylene furan dicarboxylate chain segment; m is the number of repeating units of a polybutylene carbonate chain segment;
and m and n are natural numbers, and the value range of m and n is any value between 20 and 300.
Has the advantages that:
under the double effects of an efficient composite catalyst and a one-pot experiment, the polyfurandicarboxylic acid-carbonic acid-butanediol ester (PBCF) with high viscosity (1.2-2.0 dL/g) and low melting index (3-20 g/10 min) can be quickly prepared in a short time, the comprehensive performance is excellent, the method can greatly shorten the production period of PBCF, greatly reduce the energy consumption, effectively reduce the resource waste and has a large-scale production prospect.
Drawings
Figure 1 is a 1H-NMR spectrum of the aromatic-aliphatic PBCF copolyester prepared in example 5 of the present invention.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention should not be limited to the following examples.
The intrinsic viscosity and melt index in the following examples were measured as follows:
intrinsic viscosity: 0.2g of biomass aromatic-aliphatic PBCF copolyester is dissolved in 20 ml of phenol-1, 2-tetrachloroethane mixed solution with the mass ratio of 1, and the solution is measured in a water bath at 25 ℃ by a one-point method, and the intrinsic viscosity is calculated by the following formula:
wherein: eta r : relative viscosity, η sp : increase in specific viscosity, t 0 : time of solvent flow out, t 1 : polymer solution flow-out time, c: polymer solution concentration.
Melt index: based on the national standards GBT3682.1 and 3682.2, it is characterized by a melt index tester (FR-1811A).
Yield =100% x actual amount of target product/theoretical amount of target product.
Example 1 (preparation of novel Complex catalyst)
Sodium methoxide (5.4 g, 0.1mol), tetrabutyl titanate (34.0g, 0.1mol), triphenyl phosphate (32.6 g, 0.1mol) and tetraethoxysilane (10.4g, 0.05mol) are sequentially placed into a single-neck flask filled with absolute ethyl alcohol (230.4g, 5 mol), reflux stirring reaction is carried out for 3 hours at the temperature of 80 ℃ to obtain an intermediate product, a certain amount of deionized water is slowly dripped to continue reaction for 2 hours, heating is stopped, cooling is fully carried out, suction filtration is carried out, and vacuum drying is carried out to obtain a white solid, namely the novel composite catalyst C 1 。
Example 2 (preparation of novel composite catalyst)
Sequentially putting sodium ethoxide (6.8g, 0.1mol), tetraisopropyl titanate (28.4g, 0.1mol), triethyl phosphate (18.2g, 0.1mol) and tetraethoxysilane (10.4g, 0.05mol) into a single-neck flask filled with absolute ethyl alcohol (230.4g, 5 mol), carrying out reflux stirring reaction at 60 ℃ for 3 hours to obtain an intermediate product, slowly dropwise adding a certain amount of deionized water, continuing the reaction for 2 hours, stopping heating, fully cooling, carrying out suction filtration, and carrying out vacuum drying to obtain a white solid, namely the novel composite catalyst C 2 。
Example 3 (preparation of novel Complex catalyst)
Sodium methoxide (6.8g, 0.1mol), tetrabutyl titanate (170.0g, 0.5mol), triphenyl phosphate (65.2g, 0.2mol) and tetraethoxysilane (4.2g, 0.02mol) are sequentially placed into a single-neck flask filled with absolute ethyl alcohol (138.2g, 3mol), reflux stirring reaction is carried out for 3 hours at the temperature of 80 ℃ to obtain an intermediate product, a certain amount of deionized water is slowly dripped into the intermediate product, the reaction is continuously carried out for 2 hours, heating is stopped, full cooling is carried out, suction filtration is carried out, and vacuum drying is carried out to obtain a white solid, namely the novel composite catalyst C 3 。
Example 4 (preparation of novel composite catalyst)
Sequentially putting sodium hydroxide (4.0g, 0.1mol), tetrabutyl titanate (340.3g, 1mol), triphenyl phosphate (163.1g, 0.5mol) and tetraethoxysilane (6.2g, 0.03mol) into a single-neck flask filled with absolute ethyl alcohol (184.3g, 4mol), refluxing and stirring at 80 ℃ for 3 hours to obtain an intermediate product, slowly dropwise adding a certain amount of deionized water, continuing to react for 2 hours, stopping heating, fully cooling, performing suction filtration, and performing vacuum drying to obtain a white solid, namely the novel composite catalyst C 4 。
Example 5 preparation of aromatic-aliphatic copolyester PBCF
(1) Esterification reaction: under the protection of nitrogen atmosphere, 1015g of dimethyl carbonate, 1289g of dimethyl 2, 5-furandicarboxylate, 1514g of 1, 4-butanediol and 3.5g of composite catalyst C 1 And (3) adding the materials into a 5L reaction kettle together, heating the kettle to 160 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: and (3) closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air inflow, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1h when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) And (3) final polycondensation reaction: heating the temperature in the kettle to 220 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, enabling the torque to reach about 32 N.m after the reaction is carried out for 4 hours, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 97.1%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 57; the intrinsic viscosity is 1.13dL/g; the melt index at 190 ℃ was 9.2g/10min.
Water-cooling granulation: the aromatic-aliphatic polycarbonate copolymer is cooled and drafted by water and then directly enters a granulator for granulation, and the obtained master batch is dried in a vacuum oven at 60 ℃ for 24 hours to remove water.
Example 6 (preparation of aromatic-aliphatic copolyester PBCF)
(1) Esterification reaction: under the protection of nitrogen atmosphere, 1015g of dimethyl carbonate, 1093g of 2, 5-furandicarboxylic acid, 1514g of 1, 4-butanediol and 3.5g of composite catalyst C 2 Adding the mixture into a 5L reaction kettle, heating the kettle to 180 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air input, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1 hour when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) Final polycondensation reaction: heating the temperature in the kettle to 220 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, after the reaction is carried out for 5 hours, enabling the torque to reach about 32 N.m, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 98.3%; the molar ratio of aromatic polyester structural units to aliphatic structural units is 52; the intrinsic viscosity is 0.82dL/g; the melt index at 190 ℃ was 17.3g/10min.
Water-cooling granulation: the aromatic-aliphatic PBCF copolyester is cooled and stretched by water and then directly enters a granulator for granulation, and the obtained master batch is dried in a vacuum oven at 60 ℃ for 24 hours to remove moisture.
Example 7 (preparation of aromatic-aliphatic copolyester PBCF)
(1) Esterification reaction: under the protection of nitrogen atmosphere, 741g of dimethyl carbonate, 1289g of dimethyl 2, 5-furandicarboxylate, 1577g of 1, 4-butanediol and 3.5g of composite catalyst C 3 And (3) adding the materials into a 5L reaction kettle together, heating the kettle to 160 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air input, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1 hour when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) Final polycondensation reaction: heating the temperature in the kettle to 220 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, wherein the torque of the reaction reaches about 32 N.m after 4 hours of reaction, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 95.0%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 66; the intrinsic viscosity is 1.45dL/g; the melt index at 190 ℃ was 3.0g/10min.
Water-cooling granulation: the aromatic-aliphatic PBCF copolyester is cooled and stretched by water and then directly enters a granulator for granulation, and the obtained master batch is dried in a vacuum oven at 60 ℃ for 24 hours to remove moisture.
Example 8 preparation of aromatic-aliphatic copolyester PBCF
(1) Esterification reaction: in that741g of dimethyl carbonate, 1289g of 2, 5-furandicarboxylic acid, 1577g of 1, 4-butanediol and 3.5g of composite catalyst C under the protection of nitrogen atmosphere 1 Adding the materials into a 5L reaction kettle together, heating the temperature in the kettle to 160 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: and (3) closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air inflow, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1h when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) And (3) final polycondensation reaction: heating the temperature in the kettle to 230 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, wherein the torque of the reaction reaches about 32 N.m after 6 hours of reaction, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 95.4%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 60; the intrinsic viscosity is 1.39dL/g; the melt index at 190 ℃ was 3.4g/10min.
Water-cooling granulation: the aromatic-aliphatic PBCF copolyester is cooled by water, drafted and directly enters a granulator for granulation, and the obtained master batch is placed in a vacuum oven at 60 ℃ for drying for 24 hours to remove moisture.
Example 9 (preparation of aromatic-aliphatic copolyester PBCF)
(1) Esterification reaction: under the protection of nitrogen atmosphere, 1427g of dimethyl carbonate, 1289g of 2, 5-furandicarboxylic acid, 2366g of 1, 4-butanediol and 3.5g of composite catalyst C 1 Adding the mixture into a 5L reaction kettle, heating the kettle to 180 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: and (3) closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air inflow, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1h when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) And (3) final polycondensation reaction: heating the temperature in the kettle to 230 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, reacting for 3 hours until the torque reaches about 32 N.m, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 97.2%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 47; the intrinsic viscosity is 1.15dL/g; the melt index at 190 ℃ was 6.6g/10min.
Water-cooling granulation: the aromatic-aliphatic PBCF copolyester is cooled and stretched by water and then directly enters a granulator for granulation, and the obtained master batch is dried in a vacuum oven at 60 ℃ for 24 hours to remove moisture.
Example 10 (preparation of aromatic-aliphatic copolyester PBCF)
(1) Esterification reaction: under the protection of nitrogen atmosphere, 1427g of dimethyl carbonate, 1093g of dimethyl 2, 5-furandicarboxylate, 2366g of 1, 4-butanediol and 3.5g of composite catalyst C were added 1 Adding the materials into a 5L reaction kettle together, heating the temperature in the kettle to 160 ℃, preserving the temperature for 1h, and finishing the esterification reaction.
(2) Pre-polycondensation reaction: closing the esterification device, opening the polycondensation device, raising the temperature in the kettle to 190 ℃, controlling the air input, slowly increasing the vacuum degree in the kettle, maintaining the pressure for 1 hour when the vacuum degree in the reaction kettle is 500Pa, and finishing the pre-polycondensation reaction.
(3) And (3) final polycondensation reaction: heating the temperature in the kettle to 210 ℃, completely closing the air inlet valve, reducing the pressure in a certain period of time to high vacuum to perform final polycondensation reaction, wherein the torque of the reaction reaches about 32 N.m after 6 hours of reaction, closing a vacuum device, and extruding PBCF in a molten state by using inert gas; wherein: the yield is 97.4%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 42; the intrinsic viscosity is 0.90dL/g; the melt index at 190 ℃ was 11.4g/10min.
Water-cooling granulation: the aromatic-aliphatic PBCF copolyester is cooled by water, drafted and directly enters a granulator for granulation, and the obtained master batch is placed in a vacuum oven at 60 ℃ for drying for 24 hours to remove moisture.
Comparative example 1 (preparation of aromatic-aliphatic PBCF copolyester with sodium methoxide as catalyst)
PBCF copolyester is prepared by the same method as that of the embodiment 9, except that single-component alkali metal catalyst sodium methoxide is used as a reaction catalyst, the torque reaches about 21 N.m after 82 hours, the increase is avoided, and the trend is reduced; wherein: the yield is 32.1%; the molar ratio of aromatic polyester structural units to aliphatic structural units is 46; the intrinsic viscosity is 0.54dL/g; the melt index at 190 ℃ was 32.4g/10min.
Comparative example 2 preparation of aromatic-aliphatic PBCF copolyester with tetrabutyl titanate as catalyst
PBCF copolyester is prepared by the same method as that of the embodiment 9, except that single-component titanate catalyst tetrabutyl titanate is used as a reaction catalyst, and the torque reaches about 32 N.m after 41 hours; wherein: the yield is 55.7%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 42; the intrinsic viscosity is 1.30dL/g; the melt index at 190 ℃ was 6.6g/10min.
Comparative example 3 preparation of aromatic-aliphatic PBCF copolyester with Triphenyl phosphate as catalyst
PBCF copolyester was prepared in the same manner as in example 9, except that triphenyl phosphate, a single-component phosphate catalyst, was used as a reaction catalyst for preparing aromatic-aliphatic PBCF copolyester, and dimethyl carbonate was largely distilled off at the esterification stage, and no product was obtained at the end.
Comparative example 4 (Ethyl orthosilicate as catalyst for aromatic-aliphatic PBCF copolyester)
PBCF copolyester is prepared by the same method as in example 9, except that single-component ethyl orthosilicate is used as a reaction catalyst for preparing aromatic-aliphatic PBCF copolyester, and dimethyl carbonate is evaporated out in a large amount in the esterification stage, so that a product is not obtained finally.
Comparative example 5 (preparation of aromatic-aliphatic PBCF copolyester with sodium methoxide, triphenyl phosphate and ethyl orthosilicate composite catalyst)
PBCF copolyester is prepared by the same method as that of the embodiment 9, except that the composite catalyst is prepared by using sodium methoxide, triphenyl phosphate and ethyl orthosilicate and is used for preparing aromatic-aliphatic PBCF copolyester, and the torque reaches about 18 N.m after 62 hours, so that the PBCF copolyester is not increased and has a reduction trend; wherein: the yield is 43.4%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 47; the intrinsic viscosity is 0.81dL/g; the melt index at 190 ℃ was 30.4g/10min.
Comparative example 6 preparation of aromatic-aliphatic PBCF copolyester with tetrabutyl titanate, triphenyl phosphate and tetraethoxysilane composite catalyst
PBCF copolyester is prepared by the same method as that of the embodiment 9, except that tetrabutyl titanate, triphenyl phosphate and ethyl orthosilicate are used for preparing a composite catalyst for preparing aromatic-aliphatic PBCF copolyester, and the torque reaches about 32 N.m after 33 hours; wherein: the yield is 69.3%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 47; the intrinsic viscosity is 1.20dL/g; the melt index at 190 ℃ was 10.1g/10min.
Comparative example 7 preparation of aromatic-aliphatic PBCF copolyester with titanate, carbonate, phosphoric acid and tetraethoxysilane composite catalyst
PBCF copolyester is prepared by the same method as that of example 9, except that the titanium composite catalyst (titanate + carbonate + phosphoric acid + ethyl orthosilicate) described in patent CN114672005 is used for preparing aromatic-aliphatic PBCF copolyester, and the torque reaches about 32 N.m after 71 hours; wherein: the yield is 55.2%; the molar ratio of the aromatic polyester structural units to the aliphatic structural units is 40; the intrinsic viscosity is 1.14dL/g; the melt index at 190 ℃ was 12.2g/10min.
TABLE 1 results of experimental preparation of PBCF
And (4) analyzing results:
as can be seen from Table 1, examples 5 to 10 are compared with comparative examples 1 to 6: when the novel composite catalyst is used for preparing PBCF, the polymerization time can be obviously shortened, but the non-composite catalyst has poor catalytic effect, and the biomass PBCF copolyester with low melting index and high viscosity can be obtained only by prolonging the reaction time. And example 9 compared to comparative example 7: when the titanium composite catalyst suitable for PBAT synthesis is used for preparing PBCF, the catalytic effect is similar to that of the non-composite catalyst described in the patent, the catalytic effect is poor, and huge energy consumption loss is caused when the titanium composite catalyst is used for large-scale industrial production.
Claims (10)
1. A method for preparing polyfuran dicarboxylic acid-carbonic acid-butanediol ester is characterized in that,
adding 2, 5-furandicarboxylic acid or dimethyl ester thereof, dimethyl carbonate, 1, 4-butanediol and a composite catalyst into a reaction kettle together according to a certain proportion, and carrying out esterification or ester exchange reaction, pre-polycondensation reaction and final polycondensation reaction under the action of the composite catalyst to prepare polyfurandicarboxylic acid-carbonic acid-butanediol ester; the dosage of the composite catalyst is 0.01 to 0.5 percent of the total weight of the 2, 5-furandicarboxylic acid or the dimethyl ester thereof, the dimethyl carbonate and the 1, 4-butanediol in the reaction system;
the preparation raw materials of the composite catalyst comprise alkali metal, titanate, phosphate and ethyl orthosilicate; the molar ratio of the alkali metal to the titanate is 1-1; the molar ratio of the alkali metal to the phosphate is 1 to 1; the molar ratio of the alkali metal to the tetraethoxysilane is 1.
2. The process according to claim 1, wherein the molar ratio of the dimethyl carbonate to the 2, 5-furandicarboxylic acid or the dimethyl ester thereof is 1; the ratio of the molar weight of the ester group or the sum of the molar weight of the ester group and the molar weight of the carboxyl group to the molar weight of the hydroxyl group in the reaction system in the reaction kettle is 1-2.5.
3. The preparation method according to claim 1, wherein the composite catalyst is prepared by the following method:
adding alkali metal, titanate, phosphate and tetraethoxysilane into absolute ethyl alcohol, and reacting for no more than 4 hours at the temperature of 30-80 ℃;
step two, adding deionized water, and continuously reacting for 2-3 h;
and step three, cooling the reactant to room temperature, filtering, and drying in vacuum to obtain a white solid, namely the composite catalyst.
4. The method according to claim 3, wherein the alkali metal is at least one of sodium methoxide, sodium ethoxide, sodium hydroxide, and sodium acetylacetonate; the titanate is at least one of diethyl titanate, tetra-tert-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate; the phosphate is at least one of triphenyl phosphite, triphenyl phosphate and triethyl phosphate.
5. The method according to claim 3, wherein the molar ratio of the alkali metal to the absolute ethanol is 1.
6. The preparation method according to claim 1, wherein the esterification reaction temperature is 110-180 ℃ and the esterification reaction time is 2-8 h.
7. The method according to claim 6, wherein the pre-polycondensation reaction temperature is 180-200 ℃ and the pre-polycondensation reaction time is not less than 1h.
8. The method according to claim 7, wherein the final polycondensation temperature is 200 to 260 ℃ and the reaction time is not less than 1 hour.
9. The method according to claim 8, wherein the degree of vacuum in the reaction vessel is gradually increased in the pre-polycondensation reaction, and the pressure is maintained for not less than 1 hour when the degree of vacuum is 500 Pa; the pressure of the vacuum environment in the reaction kettle of the final polycondensation reaction is less than 200Pa.
10. A polyfurandicarboxylic acid-butylene carbonate having a structure represented by the following formula, which is produced by the production method according to any one of claims 1 to 9:
wherein n is the number of repeating units of a polybutylene furan dicarboxylate chain segment; m is the number of repeating units of a polybutylene carbonate chain segment;
and m and n are natural numbers, and the value range of m and n is 20-300.
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