CN114656624A - Multi-block copolymer and preparation method thereof - Google Patents
Multi-block copolymer and preparation method thereof Download PDFInfo
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- CN114656624A CN114656624A CN202210362220.3A CN202210362220A CN114656624A CN 114656624 A CN114656624 A CN 114656624A CN 202210362220 A CN202210362220 A CN 202210362220A CN 114656624 A CN114656624 A CN 114656624A
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 22
- 150000002148 esters Chemical group 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- 239000004611 light stabiliser Substances 0.000 claims description 12
- -1 dihydroxyalkyl furandicarboxylate Chemical compound 0.000 claims description 11
- 229920006030 multiblock copolymer Polymers 0.000 claims description 11
- 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 10
- 230000008569 process Effects 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 5
- 239000000806 elastomer Substances 0.000 claims description 5
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- YHEPZZFDBQOSSN-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate;1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1.C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 YHEPZZFDBQOSSN-UHFFFAOYSA-N 0.000 claims description 2
- LLJOGUQSRXUDCC-UHFFFAOYSA-N methyl formate Chemical compound COC=O.COC=O LLJOGUQSRXUDCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 26
- 125000001931 aliphatic group Chemical group 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
Images
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
A multi-block copolymer and its preparation method, 2, 5-furan dicarboxylic acid dimethyl ester and micromolecular diol, polyether mixed ester exchange reaction, get furan dicarboxylic acid dihydroxy alkyl ester; carrying out a second ester exchange reaction on the furan dicarboxylic acid dihydroxy alkyl ester and the 2, 5-furan dicarboxylic acid dimethyl ester to obtain a prepolymer; and (3) carrying out polycondensation on the prepolymer, wherein the polycondensation temperature is 200-220 ℃, and the polycondensation time is 1-6 hours. The preparation method has the advantages of low reaction temperature, low energy consumption, less side reaction, light product color, adjustable performance and the like, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of multi-block copolymers, and relates to a multi-block copolymer based on 2, 5-furan dimethyl diformate polyester and aliphatic polyether and a preparation method thereof.
Background
While traditional polymeric materials provide great convenience to human life, their enormous production and use have led to a range of resource and environmental problems. On the one hand, most of the raw materials for preparing the traditional polymer materials are from non-renewable petrochemical resources, such as polyethylene, polypropylene and polyethylene terephthalate, wherein the annual output of only PET can reach over sixty thousand tons and is in an increasing trend year by year. On the other hand, the large consumption of petrochemical resources, the greenhouse effect caused by combustion, and the non-biodegradability of some petrochemical products pose serious environmental problems. Therefore, development and utilization of renewable resources that can partially replace petrochemical resources have led to sustainable development of chemical and energy industries, and have become a common vision in all countries of the world.
The bio-based polymer material can effectively reduce environmental pollution and promote sustainable development, wherein the advantages of bio-based polyester in raw material sources, environmental benefits and energy consumption are widely paid attention to. Dimethyl 2, 5-furandicarboxylate (DMFD) can be produced by conversion of biomass feedstock and DMFD can be reacted with a diol to produce a polyester having a furan ring structure. Melt polycondensation has been widely used for polyester synthesis as an efficient and economical polymerization process.
Compared with the traditional terephthalic acid-based polyester, the furan ring structure in the DMFD-based polyester is easy to be oxidized and degraded at high temperature, and the prepared furan ring polyester has dark color and low molecular weight due to the fact that FDCA contains partial glycosyl impurities; although such polyesters have properties similar to terephthalic acid-based polyesters, the lack of toughness greatly limits their use as a replacement for conventional polyesters. The current research mainly refers to the high-temperature (more than or equal to 260 ℃) melt polycondensation technology of the traditional polyester, on one hand, the energy consumption is high, and on the other hand, the color of the product is inevitably deepened; there have been few reports of the research and production of polycondensation processes under relatively mild, low temperature conditions. Therefore, the research and preparation of the high molecular weight and light color DMFD-based polyester with certain toughness have certain scientific and application significance.
Disclosure of Invention
The technical problem to be solved is as follows: in view of the above-mentioned drawbacks, the present invention provides a multiblock copolymer based on dimethyl 2, 5-furandicarboxylate polyester and aliphatic polyether and a method for preparing the same. By changing the traditional polycondensation process, the 2, 5-furandicarboxylic acid-alicyclic/aliphatic glycol polyester hard segment and the aliphatic polyether soft segment are copolymerized under the condition of relatively low temperature, so that the thermoplastic plastic with high gas barrier property, high toughness and high mechanical strength can be obtained, the high-strength and high-resilience polyester elastomer can be obtained, and different application requirements are met.
The technical scheme is as follows: a multi-block copolymer having the structural formula:
wherein m and n are the polymerization degrees of respective blocks respectively, m is an integer not less than 40, and n is an integer from 0 to 40; r1Is selected from-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2OCH2CH2-、-CH2C(CH3)2CH2-、
At least one of; r2Is selected from-CH2CH2-、-CH2CH(CH3)O-、-CH2CH2CH2CH2At least one of O < - >; p is an integer of 4 to 60.
When used as a thermoplastic, R in the multiblock copolymer1is-CH2CH2-and-CH2CH2CH2CH2-，R2is-CH2CH2-; r in the multiblock copolymer when used as a polyester elastomer1is-CH2CH2CH2CH2-，R2is-CH2CH2CH2CH2O-。
The preparation method of the multi-block copolymer comprises the following steps: (1) in the presence of a catalyst A, carrying out mixed ester exchange reaction on dimethyl 2, 5-furandicarboxylate, micromolecular diol and polyether to obtain dihydroxyalkyl furandicarboxylate, wherein the micromolecular diol is R1The corresponding diol, the molar ratio of dimethyl 2, 5-furandicarboxylate to alcohol/ether hydroxyl is (1.4-3.0): 1.0, wherein the catalyst A is tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, dibutyltin oxide, stannous octoate, stannous oxalate or lanthanum acetylacetonate, and accounts for 0.2-0.8 per mill of the total mass of reactants; (2) carrying out a second ester exchange reaction on the furan dicarboxylic acid dihydroxy alkyl ester obtained in the step (1) and 2, 5-furan dicarboxylic acid dimethyl ester to obtain a prepolymer, wherein the furan dicarboxylic acid dihydroxy alkyl ester/2, 5-furan dicarboxylic acid dimethyl esterThe molar ratio is (2.0-1.0) to 1.0, and the reaction temperature is 150-; (3) and (3) carrying out polycondensation on the prepolymer obtained in the step (2) under the action of a catalyst B, wherein the polycondensation temperature is 200-220 ℃, the polycondensation time is 1-6 hours, the catalyst B is germanium oxide, lithium acetylacetonate, antimony trioxide, tetrabutyl titanate or tetraisopropyl titanate, and the catalyst B accounts for 0.2-0.8 per mill of the total mass of reactants.
Preferably, the step (1) is: under the condition of catalyst A and auxiliary agent, 2, 5-furan dicarboxylic acid dimethyl ester is mixed with micromolecular diol and polyether to carry out ester exchange reaction, and when the collected distillate reaches not less than 95 percent of theoretical value, the first step reaction is finished to obtain furan dicarboxylic acid dihydroxy alkyl ester; the catalyst A accounts for 0.3-0.5 per mill of the total mass of reactants; the dosage of the assistant is 0.01-1 wt% of the total amount of the monomers, the assistant is at least one of a heat stabilizer and a light stabilizer, the heat stabilizer is dibutyltin oxide and trimethyl phosphate, and the light stabilizer is light stabilizer 944, light stabilizer 622, light stabilizer 770, light stabilizer 292 or light stabilizer 783.
Preferably, the step (2) is: and (2) continuously adding 2, 5-dimethyl furandicarboxylate with equal molar weight into the dihydroxyalkyl furandicarboxylate obtained in the step (1), continuously stirring at the reaction temperature of 150-220 ℃ for 1-5 hours to obtain an oligomer, and after the reaction is finished, maintaining the reaction temperature to perform the step (3).
Preferably, the step (3) is: and (3) adding a catalyst B into the oligomer obtained in the step (2), controlling the pressure to be 40 +/-5 Pa within half an hour, and carrying out vacuum polycondensation for 2-8 hours.
Has the advantages that: according to the invention, dimethyl furandicarboxylate serving as a biomass resource is taken as a raw material, short-chain diol and flexible polyether are introduced, an improved low-temperature three-step ester exchange-polycondensation process is adopted to obtain a multi-block copolymer of 2, 5-dimethyl furandicarboxylate-alicyclic/aliphatic diol polyester and aliphatic polyether, and the molecular weight of the copolymer prepared under a low-temperature condition is equivalent to that of a traditional high-temperature method; meanwhile, the regulation and control of the thermoplastic plastic with high modulus, high toughness and high mechanical strength (40-80 MPa) to the thermoplastic polyester elastomer material with high strength (10-40 MPa) and high recovery performance (more than 80 percent of recovery rate) can be obtained. The preparation method has the advantages of low reaction temperature, low energy consumption, less side reaction, light product color, adjustable performance and the like, and is beneficial to industrial application.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum diagram of a multi-block copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether prepared by the present invention.
FIG. 2 is a differential scanning calorimetry chart of a multi-block copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether prepared according to the present invention.
FIG. 3 is an infrared spectrum of a multi-block copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether prepared according to the present invention, wherein (a) the differential scanning calorimetry cooling curve of the block copolymer with different proportions; (b) differential scanning calorimetry temperature rise curves of block copolymers of different proportions.
FIG. 4 is a stress-strain curve of a multiblock copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether prepared according to the present invention.
FIG. 5 is a cycle pull and recovery curve for a multi-block copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether prepared in accordance with the present invention, wherein (a) the cycle pull curve for a PETF-30 sample; (b) elastic recovery curve during cyclic pull-up of PETF-30 sample.
Detailed Description
The invention is further illustrated by the following specific examples.
The technical solution of the present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention. In the examples, all percentages are by weight unless otherwise indicated.
The reaction equation is as follows, so as to conveniently, simply and efficiently obtain the block copolyester:
the preparation method of the segmented copolymer of the 2, 5-furandicarboxylic acid polyester and the aliphatic polyether comprises the following steps:
(1) in the presence of a catalyst A, carrying out mixed ester exchange reaction on dimethyl 2, 5-furandicarboxylate, micromolecular diol and polyether to obtain dihydroxyalkyl furandicarboxylate, wherein the molar ratio of the dimethyl to the alcohol/ether hydroxyl is (1.4-3.0) to 1.0.
(2) And (2) carrying out a second-step ester exchange reaction on the furan dicarboxylic acid dihydroxy alkyl ester obtained in the step (1) and a proper amount of 2, 5-furan dicarboxylic acid dimethyl ester to obtain a prepolymer, wherein the molar ratio of the furan dicarboxylic acid dihydroxy alkyl ester to the 2, 5-furan dicarboxylic acid dimethyl ester is (2.0-1.0) to 1.0. The reaction temperature is 150-220 ℃.
(3) And (3) carrying out polycondensation on the prepolymer obtained in the step (2) under the action of a catalyst B, wherein the polycondensation temperature is 200-220 ℃, the catalyst is antimony trioxide, lithium acetylacetonate, zinc acetate, germanium oxide and the like, and the dosage of the catalyst accounts for 0.2-0.8 per mill of the total mass of reactants.
In order to increase the molecular weight
The step (1) is as follows:
adding dimethyl furandicarboxylate, low molecular diol and polyether diol into an esterification kettle equipped with a rectifying tower according to a certain proportion to perform ester exchange reaction. Preferably, the transesterification temperature is 160 to 180 ℃. The ester exchange temperature is too low (< 180 ℃), the ester exchange is incomplete (the esterification rate is less than 100%), the subsequent polycondensation is influenced, and the molecular weight is reduced; the excessive high temperature (more than 180 ℃) of the ester exchange reaction can increase the loss of low molecular diol, cause the unbalance of the mixture ratio of reactants and influence the growth of molecular weight.
② under the reaction temperature of 160-180 ℃, continuously stirring and the reaction time is 3-7 hours, ensuring that the distillate accounts for more than 95% of the theoretical value, stopping the reaction, then cooling to 60 ℃, adding part of dimethyl furandicarboxylate again, and continuing the reaction to obtain the oligomer of the block copolyester.
In order to improve the toughening effect, the molecular weight of the aliphatic polyether soft segment is preferably 500-2000 g/mol.
When the molecular weight of the soft segment of the aliphatic polyether is lower than 500g/mol, the flexibility provided in the unit length is insufficient, the thermal stability is poor, and the toughness of the segmented copolymer material is not favorably improved; when the molecular weight of the aliphatic polyether soft segment exceeds 2000g/mol, the unit length is too large, so that the compatibility of the aliphatic polyether soft segment and the 2, 5-furandicarboxylic acid polyester hard segment is too poor, and the melting point of the material is also greatly reduced. These are not favorable for improving the mechanical property of the material.
In order to lower the polycondensation temperature (270 ℃ → 220 ℃), the above step (2) is:
and (2) carrying out a second-step ester exchange reaction on the dihydroxyalkyl furandicarboxylate obtained in the step (1) and a proper amount of dimethyl 2, 5-furandicarboxylate to obtain a prepolymer with a partial ester group end capping, wherein the molar ratio of the dihydroxyalkyl furandicarboxylate to the dimethyl 2, 5-furandicarboxylate is (2.0-1.0) to 1.0. Preferably, the molar ratio of the dihydroxyalkyl furandicarboxylate to the dimethyl 2, 5-furandicarboxylate is (1.2-1.0) to 1.0. The molar ratio of hydroxyl and methyl ester in the system is close to 1: 1 under the condition of the proportion, compared with the traditional high-temperature polycondensation for removing high-boiling-point glycol, such as ethylene glycol, propylene glycol, butanediol and other micromolecular diols, the invention mainly generates ester exchange reaction for removing low-boiling-point methanol with relatively high activity in the polycondensation process, the reaction activation energy of the process is lower, and the high-molecular-weight polyester can be obtained at relatively lower temperature (less than or equal to 220 ℃).
Example 1:
preparation of a multiblock copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether:
into a flask equipped with a constant-temperature overhead stirrer, a rectifying column, a temperature measuring and nitrogen introducing device were charged 0.35mol (64.4g) of dimethyl 2, 5-furandicarboxylate, 0.70mol (43.4g) of ethylene glycol, 0.0423mol (42.30g) of polytetrahydrofuranediol
0.05g of tetraisopropyl titanate, reacted at 160 ℃ under nitrogenThe reaction time is 2 hours, the reaction time is 1 hour at 170 ℃, and the reaction time is 2 hours at 180 ℃ to obtain the ester exchange product.
The temperature is reduced to 140 ℃ and 150 ℃, 0.38mol (69.92g) of 2, 5-furandicarboxylic acid dimethyl ester is continuously added, the temperature is increased to 160 ℃, and the temperature is increased to 220 ℃ under the nitrogen atmosphere at the heating rate of 10 ℃/h. An oligomer is obtained.
Cooling to 170 ℃, adding 0.1g of antimony trioxide, stirring, gradually heating to 200 ℃, pumping the system pressure to 40 +/-5 Pa within 30 minutes, then increasing the temperature to 220 ℃, and controlling the temperature of the distillation head at 120-150 ℃ in the process. The reaction was stopped when the stirrer shaft torque no longer increased.
The final product is thermoplastic with excellent performance, and the tensile strength is higher than 50MPa and the elongation at break is close to 50 percent according to the combination of tensile data.
Example 2:
preparation of a multiblock copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether:
0.26mol (47.84g) of dimethyl 2, 5-furandicarboxylate, 0.52mol (39.52g) of 1, 3-propanediol and 0.0416mol (83.20g) of polyethylene glycol (PEG, M) were placed in a flask equipped with a thermostatic overhead stirrer, a rectifying column, a temperature measuring and nitrogen introducing device-n-2000 g/mol), 0.1g zinc acetate, under nitrogen atmosphere at 160 ℃ for 2 hours, 170 ℃ for 1 hour, 180 ℃ for 2 hours to obtain the transesterification product.
The temperature is reduced to 140 ℃ and 150 ℃, 0.29mol (53.36g) of 2, 5-furandicarboxylic acid dimethyl ester is continuously added, the temperature is increased to 160 ℃, and the reaction is carried out to 200 ℃ at the heating rate of 10 ℃/h under the nitrogen atmosphere. An oligomer is obtained.
Cooling to 170 ℃, adding 0.15g of lanthanum acetylacetonate, stirring, gradually heating to 200 ℃, pumping the system pressure to 40 +/-5 Pa within 30 minutes, then increasing the temperature to 220 ℃, and controlling the temperature of the distillation head at 120-150 ℃ in the process. The reaction was stopped when the stirrer shaft torque no longer increased.
The final product is a thermoplastic elastomer, and the tensile strength is about 20MPa and the elongation at break is close to 450% by combining the tensile data in the figure, and the elastic recovery rate is kept above 85% through 10-cycle tensile experiments, so that the final product is a bio-based polyester elastomer material with excellent performance.
Example 3:
preparation of a multiblock copolymer of 2, 5-furandicarboxylic acid polyester and aliphatic polyether:
a flask equipped with a constant-temperature overhead stirrer, a rectifying column, a temperature measuring and nitrogen introducing device was charged with 0.26mol (47.50g) of dimethyl 2, 5-furandicarboxylate, 0.52mol (46.47g) of 1, 4-butanediol, 0.071mol (70.48g) of polypropylene glycol (PPG, M-n: 1000g/mol), and 0.05g of tetrabutyl titanate, and reacted at 160 ℃ for 2 hours, 170 ℃ for 1 hour, and 180 ℃ for 2 hours under a nitrogen atmosphere to obtain an ester-exchanged product.
The temperature is reduced to 140 ℃ and 150 ℃, 0.42mol (77.28g) of 2, 5-furandicarboxylic acid dimethyl ester is continuously added, the temperature is increased to 160 ℃, and the reaction is carried out to 190 ℃ at the heating rate of 10 ℃/h under the nitrogen atmosphere. An oligomer is obtained.
Cooling to 170 deg.C, adding 0.13g germanium oxide GeO2Stirring and gradually raising the temperature to 200 ℃, pumping the system pressure to 40 +/-5 Pa within 30 minutes, then increasing the temperature to 220 ℃, and controlling the temperature of the distillation head to be 120-150 ℃ in the process. The reaction was stopped when the stirrer shaft torque no longer increased.
The final product is a thermoplastic elastomer, and the tensile strength is about 16MPa and the elongation at break is close to 650 percent according to tensile data in the figure, and the elastic recovery rate is kept above 80 percent through 10 times of cyclic tensile experiments, so that the final product is a bio-based polyester elastomer material with excellent performance.
TABLE 1 multiblock copolymer composition based on 2, 5-furandicarboxylic acid and aliphatic polyether prepared according to the present invention and molecular weight distribution
Claims (6)
1. A multi-block copolymer characterized by the structural formula:
2. The multiblock copolymer of claim 1, wherein R is the number of R in the multiblock copolymer when used as a thermoplastic1is-CH2CH2-and-CH2CH2CH2CH2-，R2is-CH2CH2-; r in the multiblock copolymer when used as a polyester elastomer1is-CH2CH2CH2CH2-，R2is-CH2CH2CH2CH2O-。
3. A process for the preparation of a multiblock copolymer according to any of claims 1 to 2, comprising the steps of: (1) in the presence of a catalyst A, carrying out mixed ester exchange reaction on dimethyl 2, 5-furandicarboxylate, micromolecular diol and polyether to obtain dihydroxyalkyl furandicarboxylate, wherein the micromolecular diol is R1The corresponding diol, the molar ratio of dimethyl 2, 5-furandicarboxylate to alcohol/ether hydroxyl is (1.4-3.0): 1.0, wherein the catalyst A is tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, dibutyltin oxide, stannous octoate, stannous oxalate or lanthanum acetylacetonate, and accounts for 0.2-0.8 per mill of the total mass of reactants; (2) the furan dicarboxylic acid dihydroxy alkyl ester obtained in the step (1) is further mixed with 2, 5-furanCarrying out a second ester exchange reaction on dimethyl diformate to obtain a prepolymer, wherein the molar ratio of the furan dicarboxylic acid dihydroxy alkyl ester to the 2, 5-furan dicarboxylic acid dimethyl ester is (2.0-1.0): 1.0, the reaction temperature is 150-220 ℃; (3) and (3) carrying out polycondensation on the prepolymer obtained in the step (2) under the action of a catalyst B, wherein the polycondensation temperature is 200-220 ℃, the polycondensation time is 1-6 hours, the catalyst B is germanium oxide, lithium acetylacetonate, antimony trioxide, tetrabutyl titanate or tetraisopropyl titanate, and the catalyst B accounts for 0.2-0.8 per mill of the total mass of reactants.
4. The method according to claim 3, wherein the step (1) is: under the condition of catalyst A and auxiliary agent, 2, 5-furan dicarboxylic acid dimethyl ester is mixed with micromolecular diol and polyether to carry out ester exchange reaction, and when the collected distillate reaches not less than 95 percent of theoretical value, the first step reaction is finished to obtain furan dicarboxylic acid dihydroxy alkyl ester; the catalyst A accounts for 0.3-0.5 per mill of the total mass of reactants; the dosage of the assistant is 0.01-1 wt% of the total amount of the monomers, the assistant is at least one of a heat stabilizer and a light stabilizer, the heat stabilizer is dibutyl tin oxide or trimethyl phosphate, and the light stabilizer is light stabilizer 944, light stabilizer 622, light stabilizer 770, light stabilizer 292 or light stabilizer 783.
5. The method according to claim 3, wherein the step (2) is: and (2) continuously adding 2, 5-dimethyl furandicarboxylate with equal molar weight into the dihydroxyalkyl furandicarboxylate obtained in the step (1), continuously stirring at the reaction temperature of 150-220 ℃ for 1-5 hours to obtain an oligomer, and after the reaction is finished, maintaining the reaction temperature to perform the step (3).
6. The production method according to claim 3, wherein the step (3) is: and (3) adding a catalyst B into the oligomer obtained in the step (2), controlling the pressure to be 40 +/-5 Pa within half an hour, and carrying out vacuum polycondensation for 2-8 hours.
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| US20180258219A1 (en) * | 2015-09-14 | 2018-09-13 | Synvina C.V. | Process for the preparation of a polyester |
| CN108997568A (en) * | 2018-06-21 | 2018-12-14 | 浙江大学 | A kind of biological poly ester material and its preparation method and application |
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| US20180258219A1 (en) * | 2015-09-14 | 2018-09-13 | Synvina C.V. | Process for the preparation of a polyester |
| CN108997568A (en) * | 2018-06-21 | 2018-12-14 | 浙江大学 | A kind of biological poly ester material and its preparation method and application |
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| Title |
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| 刘茜;姜敏;周光远;张强;叶冲;敖玉辉;: "直接酯化法合成聚2, 5-呋喃二甲酸乙二酯", 应用化学, no. 07, 10 July 2012 (2012-07-10), pages 27 - 32 * |
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