CN118271582A - Bio-based copolyester and preparation method and application thereof - Google Patents
Bio-based copolyester and preparation method and application thereof Download PDFInfo
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- CN118271582A CN118271582A CN202410100491.0A CN202410100491A CN118271582A CN 118271582 A CN118271582 A CN 118271582A CN 202410100491 A CN202410100491 A CN 202410100491A CN 118271582 A CN118271582 A CN 118271582A
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 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 description 50
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 28
- 239000004626 polylactic acid Substances 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 20
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 19
- -1 propylene, butylene Chemical group 0.000 claims description 17
- 238000007334 copolymerization reaction Methods 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 13
- 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 11
- 230000032050 esterification Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 6
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- 229940035437 1,3-propanediol Drugs 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- JOTDFEIYNHTJHZ-UHFFFAOYSA-N furan-2,4-dicarboxylic acid Chemical compound OC(=O)C1=COC(C(O)=O)=C1 JOTDFEIYNHTJHZ-UHFFFAOYSA-N 0.000 claims description 4
- SYLAFCZSYRXBJF-UHFFFAOYSA-N furan-3,4-dicarboxylic acid Chemical compound OC(=O)C1=COC=C1C(O)=O SYLAFCZSYRXBJF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 238000013270 controlled release Methods 0.000 claims description 2
- 229920006238 degradable plastic Polymers 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 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
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 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 2
- 239000012974 tin catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 8
- CMJBUVNYQIMCQH-UHFFFAOYSA-N C(CCCC)OC(=O)C=1OC=CC1C(=O)O Chemical compound C(CCCC)OC(=O)C=1OC=CC1C(=O)O CMJBUVNYQIMCQH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002334 glycols Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- ZOVSNXYOLUSCIN-UHFFFAOYSA-N 6-methyl-6,7-dihydrofuro[2,3-f][1,4]dioxocine-4,9-dione Chemical compound O1C2=C(C=C1)C(=O)OC(COC2=O)C ZOVSNXYOLUSCIN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MMHWNKSVQDCUDE-UHFFFAOYSA-N hexanedioic acid;terephthalic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MMHWNKSVQDCUDE-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Abstract
The present disclosure relates to a bio-based copolyester, a preparation method and applications thereof. The bio-based copolyester has a first structural unit and a second structural unit; the first structural unit has a structure shown in formula I, and the second structural unit has a structure shown in formula II. The preparation method provided by the disclosure is mild in condition, and the prepared bio-based copolyester has excellent mechanical properties.
Description
Technical Field
The invention relates to the field of materials, in particular to a bio-based copolyester, a preparation method and application thereof.
Background
Polylactic acid (PLA) has been the focus of recent research on biodegradable materials because of its excellent biodegradability and biocompatibility. However, because polylactic acid has the characteristic of high brittleness, the mechanical properties (strength, modulus and the like) of the polylactic acid are obviously lower than those of petroleum-based polymer materials such as polyethylene terephthalate and the like, and the application range of the polylactic acid is severely limited. The modification effect of introducing other monomers into polylactic acid molecules to form the copolymer is good.
CN102838734a discloses that a block copolymer is prepared by copolymerizing poly (adipic acid-terephthalic acid) butanediol copolyester with polylactic acid. However, the method adopts a large amount of terephthalic acid, which is harmful to the environment.
Therefore, it is necessary to develop a polymer material which can effectively improve brittleness and mechanical properties of polylactic acid.
Disclosure of Invention
The invention aims to provide a bio-based copolyester, a preparation method and application thereof.
In one aspect of the present disclosure, a biobased copolyester is provided having a first structural unit and a second structural unit; the first structural unit has a structure shown in a formula I, and the second structural unit has a structure shown in a formula II;
wherein ring A is a furan ring;
R 1 is C2-C20 alkylene optionally substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy.
In some embodiments, R 1 is C2-C10 alkylene optionally substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy.
In some embodiments, R 1 is propylene, butylene, or pentylene optionally substituted with one or more substituents selected from methyl, ethyl, methoxy, or ethoxy.
In some embodiments, R 1 is straight chain propylene, butylene, or pentylene.
In some embodiments, the first structural unit is esterified from a dicarboxylic acid or derivative thereof and a diol, and the second structural unit is derived from polylactic acid.
In some embodiments, derivatives of the dicarboxylic acids include compounds obtained after substitution of the carboxyl hydroxyl groups in the carboxylic acids with any suitable leaving group, such as esters or acid halide compounds of the carboxylic acids, and the like.
In some embodiments, the dicarboxylic acid or derivative thereof is a furan ring-containing dicarboxylic acid or derivative thereof.
In some embodiments, the dicarboxylic acid or derivative thereof is at least one of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid, 3, 4-furandicarboxylic acid.
In some embodiments, the glycol is a C2-C20 glycol substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy.
In some embodiments, the glycol is a C2-C10 glycol substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy.
In some embodiments, the glycol is methyl, ethyl, methoxy, or ethoxy substituted propylene glycol, butylene glycol, or pentylene glycol.
In some embodiments, the glycol is one or more of 1, 3-propanediol, 1, 4-butanediol, or 1, 5-pentanediol.
In some embodiments, the glycol is 1,5 pentanediol.
In some embodiments, the bio-based copolyester has a weight average molecular weight of 16000 to 24000.
In some embodiments, the biobased copolyester comprises Amol% of the first structural units and (100-a) mole% of the second structural units, wherein a is selected from 40-60, e.g. 40, 45, 50, 55 or 60.
In another aspect of the present disclosure, a method for preparing a bio-based copolyester is provided, comprising the steps of:
(1) Carrying out esterification reaction on dicarboxylic acid or derivatives thereof and dihydric alcohol to obtain a first intermediate product;
(2) Carrying out polycondensation reaction on the first intermediate product to obtain a second intermediate product;
(3) And (3) carrying out copolymerization reaction on the second intermediate product and lactide to obtain the bio-based copolyester.
In some embodiments, in step (1), the dicarboxylic acid or derivative thereof is a furan ring-containing dicarboxylic acid or derivative thereof.
In some embodiments, the dicarboxylic acid or derivative thereof is selected from at least one of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid, 3, 4-furandicarboxylic acid.
In some embodiments, the glycol is a C2-C20 glycol substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy.
In some embodiments, the glycol is a C2-C10 glycol substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy.
In some embodiments, the glycol is selected from the group consisting of methyl, ethyl, methoxy, or ethoxy substituted propylene glycol, butylene glycol, or pentylene glycol.
In some embodiments, the glycol is one or more of 1, 3-propanediol, 1, 4-butanediol, or 1, 5-pentanediol.
In some embodiments, the glycol is 1,5 pentanediol.
The bio-based copolyester prepared by the dihydric alcohol with a longer carbon chain can have both high elastic modulus and high elongation at break.
In some embodiments, the molar ratio of the dicarboxylic acid or derivative thereof to the diol is 1 (1.0 to 2.2), for example 1:1.1, 1:1.3, 1:1.6, 1:1.9, 1:2.2.
In some embodiments, the molar ratio of the dicarboxylic acid or derivative thereof to the diol is 1 (1.4 to 2.2).
In some embodiments, in step (1), the esterification reaction employs an esterification catalyst.
In some embodiments, the esterification catalyst is selected from one or more of a titanium-based catalyst, a tin-based catalyst.
In some embodiments, the esterification catalyst in step (1) is selected from one or more of tetrabutyl titanate, tin monobutyltiiso-octoate, isopropyl titanate.
In some embodiments, the esterification catalyst in step (1) is selected from tetrabutyl titanate.
In some embodiments, the molar ratio of the dicarboxylic acid or derivative thereof to the esterification catalyst is 1 (0.0001 to 0.001), for example 1:0.00015, 1:0.0003, 1:0.0005, 1:0.0007, 1:0.0009, 1:0.001.
In some embodiments, step (1) further comprises: the esterification reaction temperature is 160-190 ℃, for example 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃.
In some embodiments, step (1) further comprises: the temperature of the esterification reaction is 170-180 ℃.
In some embodiments, step (1) further comprises: the esterification reaction time is 2.0 to 6.0 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours.
In some embodiments, step (1) further comprises: the time is 3.0-4.0 h.
In some embodiments, step (1) further comprises: the esterification reaction is carried out in the presence of an inert gas.
In some embodiments, the inert gas is selected from one or more of nitrogen, helium, argon.
In some embodiments, in step (2), the second intermediate has a weight average molecular weight of 10000-14000.
In some embodiments, in step (2), the esterification reaction is performed under reduced pressure.
In some embodiments, the esterification reaction of step (2) has a system pressure of less than or equal to 200Pa.
In some embodiments, the esterification reaction of step (2) is carried out at a system pressure of 200Pa.
In some embodiments, the temperature of the polycondensation reaction of step (2) is 180-220 ℃, e.g., 180 ℃, 185 ℃, 190 ℃, 195 ℃,200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃.
In some embodiments, the temperature of the polycondensation reaction of step (2) is 190 to 200 ℃.
In some embodiments, the polycondensation reaction in step (2) is carried out for a period of time ranging from 0.5 to 5.0 hours, for example, 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours.
In some embodiments, the polycondensation reaction in step (2) is for a period of time ranging from 2.0 to 4.0 hours.
In some embodiments, in step (3), the copolymerization employs a copolymerization catalyst.
In some embodiments, the copolymerization catalyst of step (3) is selected from tin-based catalysts.
In some embodiments, the copolymerization catalyst of step (3) is selected from stannous octoate.
In some embodiments, the molar ratio of the dicarboxylic acid or derivative thereof to the lactide is 1: (1.1-2.0), for example 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.
The molar ratio of the dicarboxylic acid or the derivative thereof to the copolymerization catalyst is 1 (0.0001-0.001).
In some embodiments, the temperature of the copolymerization reaction of step (3) is 160 to 170 ℃, e.g., 160 ℃, 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃.
In some embodiments, the time for the copolymerization reaction of step (3) is 3.0 to 8.0 hours, for example 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours.
In some embodiments, the time of the copolymerization reaction of step (3) is 4.0 to 6.0 hours.
In a third aspect, the invention provides an application of the bio-based copolyester of the first aspect or the bio-based copolyester obtained by the preparation method of the second aspect in the fields of degradable plastics, degradable fibers, agricultural mulching films and drug controlled release carriers.
Compared with the prior art, the method has the following beneficial effects: the bio-based copolyester with excellent mechanical properties is prepared by polymerizing rigid furan ring diacid and glycol with a longer carbon chain under milder conditions, and is used as a comonomer to be copolymerized with lactide, so that the effect of efficiently maintaining the mechanical strength and modulus and the glass transition temperature of the brittle polylactic acid can be realized while the brittle polylactic acid is remarkably improved.
The furan dicarboxylic acid polyester has excellent mechanical properties, and can obviously improve the brittleness of polylactic acid by copolymerizing the furan dicarboxylic acid polyester and the polylactic acid, and simultaneously maintain the mechanical strength, the modulus and the glass transition temperature of the polylactic acid.
Drawings
FIG. 1 shows a 1 H-NMR spectrum of a poly (pentanediol furandicarboxylate) (PPeF) -polyester in one embodiment of the present disclosure.
FIG. 2 is a 1 H-NMR spectrum of a poly (amyl furandicarboxylate) (PPeF) -poly (lactic acid) (PLA) copolyester in an embodiment of the disclosure.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention in any way. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present disclosure. Such structures and techniques are also described in a number of publications.
Definition of the definition
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly used in the art to which this invention belongs. For the purposes of explaining the present specification, the following definitions will apply, and terms used in the singular will also include the plural and vice versa, as appropriate.
The terms "a" and "an" as used herein include plural referents unless the context clearly dictates otherwise.
The term "about" as used herein means a range of + -20% of the numerical values thereafter. In some embodiments, the term "about" means a range of ±10% of the numerical value following that. In some embodiments, the term "about" means a range of ±5% of the numerical value following that.
Examples and figures are provided below to aid in the understanding of the invention. It is to be understood that these examples and drawings are for illustrative purposes only and are not to be construed as limiting the invention in any way. The actual scope of the invention is set forth in the following claims. It will be understood that any modifications and variations may be made without departing from the spirit of the invention.
Examples
Reagents or raw materials from which the disclosure does not explicitly describe are all conventional commercial products.
Example 1:
2, 5-furandicarboxylic acid, 1, 5-pentanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:1.4:0.001) and reacted for 6 hours under the inert atmosphere at 160 ℃. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; the reaction is carried out for 6 hours at 200 ℃ under the system pressure of 200Pa to obtain the poly (amyl furandicarboxylate) (PPeF), and the 1 H-NMR chart is shown in figure 1. The temperature is reduced to 160 ℃, then a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1,5 pentanediol and lactide is 1:1.4:1.4) is slowly added, after the lactide is dissolved, tin isooctanoate with the molar ratio of 0.001 of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (furandicarboxylic acid) pentanediol ester-polylactic acid copolyester is obtained, and the 1 H-NMR chart is shown in figure 2. The weight average molecular weight of the product is 19000, the molecular weight dispersion index is 1.73, and the mechanical properties are shown in Table 1.
Example 2:
2, 5-furandicarboxylic acid, 1, 5-pentanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:1.6:0.001) and reacted for 4 hours at 170 ℃ under inert atmosphere. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 210 ℃ under the system pressure of 200Pa to obtain the poly (amyl furandicarboxylate) (PPeF). The temperature is reduced to 160 ℃, a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1,5 pentanediol and lactide is 1:1.6:1.4) is slowly added, after the lactide is dissolved, tin isooctanoate with the molar amount of 0.001 of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (furandicarboxylic acid) pentanediol ester-polylactic acid copolyester is obtained.
Example 3:
2, 5-furandicarboxylic acid, 1, 5-pentanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:1.8:0.001) and reacted for 4 hours at 180 ℃ under inert atmosphere. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 220 ℃ under the system pressure of 200Pa to obtain the poly (amyl furandicarboxylate) (PPeF). The temperature is reduced to 160 ℃, a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1,5 pentanediol and lactide is 1:1.8:1.4) is slowly added, after the lactide is dissolved, tin isooctanoate with the molar amount of 0.001 of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (furandicarboxylic acid) pentanediol ester-polylactic acid copolyester is obtained.
Example 4:
2, 5-furandicarboxylic acid, 1, 5-pentanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:2:0.001) and reacted for 4 hours under the inert atmosphere at 190 ℃. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 220 ℃ under the system pressure of 200Pa to obtain the poly (amyl furandicarboxylate) (PPeF). The temperature is reduced to 160 ℃, a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1,5 pentanediol and lactide is 1:2:1.4) is slowly added, after the lactide is dissolved, 0.001 tin isooctanoate with the molar amount of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (furandicarboxylic acid) pentanediol ester-polylactic acid copolyester is obtained.
Example 5:
2, 5-furandicarboxylic acid, 1, 5-pentanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:2.2:0.001) and reacted for 4 hours under the inert atmosphere at 190 ℃. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 220 ℃ under the system pressure of 200Pa to obtain the poly (amyl furandicarboxylate) (PPeF). The temperature is reduced to 160 ℃, a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1,5 pentanediol and lactide is 1:2.2:1.4) is slowly added, after the lactide is dissolved, tin isooctanoate with the molar amount of 0.001 of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (furandicarboxylic acid) pentanediol ester-polylactic acid copolyester is obtained.
Example 6:
2, 5-furandicarboxylic acid, 1, 3-propanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:2.2:0.001) and reacted for 4 hours under the inert atmosphere at 190 ℃. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 220 ℃ under the system pressure of 200Pa to obtain the poly (propylene furandicarboxylate). The temperature is reduced to 160 ℃, a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid, 1, 3-propanediol and lactide is 1:2.2:1.4) is slowly added, after the lactide is dissolved, tin isooctanoate with the molar ratio of 0.001 of 2, 5-furandicarboxylic acid is added for reaction for 6 hours, and the poly (propylene furandicarboxylic acid) and poly (lactic acid) copolyester is obtained.
Example 7:
2, 5-furandicarboxylic acid, 1, 4-butanediol and tetrabutyl titanate are added into a reaction bottle according to the mol ratio (1:2.2:0.001) and reacted for 4 hours under the inert atmosphere at 190 ℃. Then pre-condensing for 0.5h under the system pressure of 50-200 Pa; and (3) reacting for 4 hours at 220 ℃ under the system pressure of 200Pa to obtain the polybutylene furan diformate. And (3) reducing the temperature to 160 ℃, slowly adding a certain amount of lactide (the molar ratio of 2, 5-furandicarboxylic acid to 1, 4-butanediol to lactide is 1:2.2:1.4), adding tin isooctanoate with the molar amount of 0.001 of 2, 5-furandicarboxylic acid after the lactide is dissolved, and reacting for 6 hours to obtain the polybutylene furandicarboxylic acid butanediol ester-polylactic acid copolyester.
Comparative example 1:
adding lactide and tin isooctanoate with the mol ratio of 1.4:0.001 into a reaction bottle, and reacting for 6 hours at 160 ℃ to obtain polylactic acid (PLLA) with the weight average molecular weight of 10000-12000.
In the embodiment and the comparative example, a microcomputer controlled universal tensile tester is used for completing the tensile test of the sample film. Table 1 shows the measurement results of the elastic modulus, elongation at break, tensile stress at break and tensile strength of the bio-based copolyester prepared in each example and the polylactic acid prepared in comparative example 1.
TABLE 1
According to the embodiment, the polylactic acid prepared in the comparative example 1 has lower elongation at break, and the bio-based copolyester with excellent mechanical properties is prepared by polymerizing the rigid furan ring dicarboxylic acid and the diol in the embodiments 1-7, and the bio-based copolyester is used as a comonomer to be copolymerized with lactide, so that the brittle polylactic acid can be remarkably improved, and meanwhile, the mechanical strength and modulus of the polylactic acid can be effectively maintained.
Further, as can be seen from table 1, the bio-based copolyester prepared using 1, 3-propanediol compared with example 6; example 7 biobased copolyester prepared using 1, 4-butanediol, the inventive example 5 poly (pentanediol furandicarboxylate) -poly (lactic acid) copolyester prepared using 1, 5-pentanediol having a longer carbon chain has excellent elongation at break and significantly improved brittleness of poly (lactic acid).
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.
Claims (10)
1. A bio-based copolyester having a first structural unit and a second structural unit; the first structural unit has a structure shown in a formula I, and the second structural unit has a structure shown in a formula II;
wherein ring A is a furan ring;
R 1 is C2-C20 alkylene optionally substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy.
2. The bio-based copolyester of claim 1, wherein R 1 is C2-C10 alkylene optionally substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy, preferably R 1 is propylene, butylene or pentylene optionally substituted with one or more substituents selected from methyl, ethyl, methoxy or ethoxy, further preferably R 1 is straight chain propylene, butylene or pentylene.
3. The biobased copolyester of claim 1, wherein said first structural unit is esterified with a dicarboxylic acid or derivative thereof and a glycol, and said second structural unit is derived from polylactic acid;
preferably, the dicarboxylic acid or derivative thereof is a dicarboxylic acid containing a furan ring or derivative thereof, preferably at least one selected from the group consisting of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid, 3, 4-furandicarboxylic acid; and/or
The diol is a C2-C20 diol substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy, preferably a C2-C10 diol substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy, more preferably methyl, ethyl, methoxy or ethoxy substituents, and is preferably propylene glycol, butylene glycol or pentylene glycol, and is preferably one or more of 1, 3-propylene glycol, 1, 4-butylene glycol or 1,5 pentylene glycol, and is preferably 1,5 pentylene glycol.
4. A biobased copolyester according to any one of claims 1 to 3, characterised in that the weight average molecular weight of said biobased copolyester is 16000-24000; and/or
The biobased copolyester comprises Amol% of a first structural unit and (100-A) mol% of a second structural unit, wherein A is selected from 40 to 60.
5. A method for preparing bio-based copolyester, comprising the following steps:
(1) Carrying out esterification reaction on dicarboxylic acid or derivatives thereof and dihydric alcohol to obtain a first intermediate product;
(2) Carrying out polycondensation reaction on the first intermediate product to obtain a second intermediate product;
(3) And carrying out copolymerization reaction on the second intermediate product and lactide to obtain the bio-based copolyester.
6. The method according to claim 5, wherein in the step (1), the dicarboxylic acid or derivative thereof is a furan ring-containing dicarboxylic acid or derivative thereof; preferably, the dicarboxylic acid or derivative thereof is selected from at least one of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid, 3, 4-furandicarboxylic acid; and/or
In step (1), the diol is a C2-C20 diol substituted with one or more substituents selected from C1-C5 alkyl or C1-C5 alkoxy, preferably a C2-C10 diol substituted with one or more substituents selected from C1-C3 alkyl or C1-C3 alkoxy, more preferably methyl, ethyl, methoxy or ethoxy substituents, and still more preferably one or more of 1, 3-propanediol, 1, 4-butanediol or 1, 5-pentanediol, preferably 1, 5-pentanediol; and/or
The molar ratio of the dicarboxylic acid or the derivative thereof to the dihydric alcohol is 1 (1.0-2.2), preferably 1 (1.4-2.2);
And/or, in the step (1), the esterification reaction adopts an esterification catalyst, preferably, the esterification catalyst is selected from one or more of titanium catalysts and tin catalysts, preferably, the esterification catalyst is selected from one or more of tetrabutyl titanate, tin monobutyltriisooctoate and isopropyl titanate, and more preferably, the esterification catalyst is selected from tetrabutyl titanate; and/or
The molar ratio of the dicarboxylic acid or the derivative thereof to the esterification catalyst is 1 (0.0001-0.001).
7. The process according to claim 5 or 6, wherein in step (1), the temperature of the esterification reaction is 160 to 190 ℃; preferably 170-180 ℃; and/or
The time of the esterification reaction is 2.0-6.0 h, preferably 3.0-4.0 h; and/or
The esterification reaction is carried out in the presence of an inert gas selected from one or more of nitrogen, helium and argon.
8. The process according to any one of claims 5 to 7, wherein in step (2), the weight average molecular weight of the second intermediate product is 10000 to 14000; and/or
The polycondensation reaction is carried out under a reduced pressure condition, preferably, the system pressure of the polycondensation reaction is less than or equal to 200Pa, preferably 200Pa; and/or
In the step (2), the temperature of the polycondensation reaction is 180-220 ℃, preferably 190-200 ℃; and/or
The polycondensation reaction time is 0.5 to 5.0 hours, preferably 2.0 to 4.0 hours.
9. The method according to any one of claims 5 to 8, wherein in step (3), the copolymerization reaction employs a copolymerization catalyst, preferably the copolymerization catalyst is selected from tin-based catalysts; stannous octoate is preferred; and/or
The mol ratio of the dicarboxylic acid or the derivative thereof to the lactide is 1:1.1-2.0; and/or
The molar ratio of the dicarboxylic acid or the derivative thereof to the copolymerization catalyst is 1 (0.0001-0.001); and/or
In the step (3), the temperature of the copolymerization reaction is 160-170 ℃; and/or
The time of the copolymerization reaction is 3.0 to 8.0 hours, preferably 4.0 to 6.0 hours.
10. Use of the bio-based copolyester according to any one of claims 1 to 4 or the bio-based copolyester obtained by the preparation method according to any one of claims 5 to 9 in the field of degradable plastics, degradable fibers, agricultural mulching films, and drug controlled release carriers.
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| Publication Number | Publication Date |
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| CN118271582A true CN118271582A (en) | 2024-07-02 |
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