CN117924678A - PBAT-based modified copolyester and preparation method thereof - Google Patents
PBAT-based modified copolyester and preparation method thereof Download PDFInfo
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- CN117924678A CN117924678A CN202410324842.6A CN202410324842A CN117924678A CN 117924678 A CN117924678 A CN 117924678A CN 202410324842 A CN202410324842 A CN 202410324842A CN 117924678 A CN117924678 A CN 117924678A
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001896 polybutyrate Polymers 0.000 title claims 19
- 239000013535 sea water Substances 0.000 claims abstract description 51
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 50
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 38
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001361 adipic acid Substances 0.000 claims abstract description 25
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims description 89
- 230000015556 catabolic process Effects 0.000 claims description 87
- 229920001223 polyethylene glycol Polymers 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 238000012643 polycondensation polymerization Methods 0.000 claims description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XXDAXUSYDPWTPK-UHFFFAOYSA-N 2-(oxo-lambda5-phosphanylidyne)acetic acid Chemical compound P(=O)#CC(=O)O XXDAXUSYDPWTPK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007385 chemical modification Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- -1 polybutylene terephthalate-adipate Polymers 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 102000004882 Lipase Human genes 0.000 description 65
- 108090001060 Lipase Proteins 0.000 description 65
- 239000004367 Lipase Substances 0.000 description 65
- 235000019421 lipase Nutrition 0.000 description 65
- 238000012360 testing method Methods 0.000 description 38
- 230000004580 weight loss Effects 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000002953 phosphate buffered saline Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 230000009471 action Effects 0.000 description 10
- 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 description 10
- 239000008363 phosphate buffer Substances 0.000 description 10
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 8
- 230000007717 exclusion Effects 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WXYNMTGBLWPTNQ-UHFFFAOYSA-N tetrabutoxygermane Chemical compound CCCCO[Ge](OCCCC)(OCCCC)OCCCC WXYNMTGBLWPTNQ-UHFFFAOYSA-N 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 241000589513 Burkholderia cepacia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polybutylene terephthalate-adipate (PBAT) based modified copolyester and a preparation method thereof. The preparation method comprises the following steps: dimethyl terephthalate or terephthalic acid, adipic acid, 1, 4-butanediol and hydrophilic monomer are mixed, and PBAT-based modified copolyester is synthesized through esterification and vacuum polycondensation. The PBAT-based modified copolyester material solves the problem that the PBAT copolyester is difficult to degrade in seawater, has excellent mechanical properties and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PBAT (polybutylene terephthalate-adipate) based modified copolyester and a preparation method thereof.
Background
Among the biodegradable polymers with the greatest commercial and technical potential, polybutylene terephthalate-adipate (PBAT) base is currently one of the most promising and popular materials. The PBAT polymer is milky white, odorless and tasteless, and is easy to be decomposed and metabolized by various microorganisms in nature or enzymes in animals and plants through composting, and finally is decomposed into carbon dioxide and water. Because of the factors of excellent comprehensive performance, reasonable cost performance, wide application and the like of PBAT, the traditional non-degradable general plastic is replaced in a plurality of fields, and the white pollution on land is relieved to a certain extent. However, the enzymatic hydrolysis process of PBAT in seawater is greatly limited due to low seawater temperature (compared with composting system), low microorganism types and numbers, and enhanced PBAT hydrophobicity due to high salt conditions, and the degradability of PBAT in seawater is poor. Typically immersed in seawater for a year, the mass loss is still less than 1%. Therefore, some scientists do not suggest their large scale application.
Patent CN116836522a discloses a seawater-degradable PBAT polyester composition and a preparation method thereof, and the prepared polyester blend has a relatively fast degradation rate in seawater by blending polyoxalate and the like with PBAT copolyester. However, the PBAT mixture prepared by the physical blending method has a problem of poor compatibility between components, and degradation of the polyoxalate component mainly occurs during degradation.
Patent CN115716910a discloses a degradable aromatic-aliphatic polyester polymer and a preparation method thereof, lactic acid is introduced into the main chain of PBAT through copolymerization, and the seawater degradation capability of the copolyester is improved. However, the hydrophilicity of the PBAT is not improved, and the improvement of the degradation capability of the PBAT is mainly due to the fact that the crystallinity is reduced due to the introduction of lactic acid units in a polymer main chain, and the problem that the PBAT chain segment is not easy to degrade still exists.
Patent CN113307959a discloses a seawater-degradable butylene succinate copolyester and a preparation method thereof, and an imine structure is introduced into a main chain of PBS, so that the seawater degradation rate of the PBS copolyester is improved. But the obtained polymer has poor toughness, the elongation at break is less than 200 percent, and the PBAT is difficult to replace.
At present, there is no PBAT-based copolyester with high degradation speed, thus being degradable by seawater and excellent in performance. In order to adapt to the development steps of society and environmental protection, development of a low-cost seawater-degradable PBAT-based copolyester and a synthesis method thereof are urgently needed, so that the low-cost seawater-degradable PBAT-based copolyester meets the increasing market demands.
Disclosure of Invention
Based on the analysis, the invention provides a PBAT-based modified copolyester and a preparation method thereof. The degradation process of polyester mainly depends on the hydrolysis of ester bonds by biological enzymes of microorganisms. In seawater, the hydrophobicity of the PBAT copolyester is enhanced due to the existence of salt, and microorganisms are not easy to enrich on the surface of the PBAT copolyester. In order to increase the adhesion of microorganisms in seawater on the surface of the degradable polyester, hydrophilic monomers such as ethylene glycol, polyethylene glycol and the like can be introduced in the polymerization process, so that the hydrophilicity of the copolyester is increased. On the other hand, the introduction of the comonomer also reduces the crystallinity of the PBT segment, further reducing the hydrophobicity of the polyester. The combined action of the two can greatly improve the seawater degradation performance of the polymer.
The invention provides a PBAT-based modified copolyester, which has excellent mechanical properties and seawater degradation properties. The copolyester with different seawater degradation performance and mechanical property can be obtained by using hydrophilic monomers with different molecular weights and regulating and controlling the content of the hydrophilic monomers in the polymer.
Meanwhile, the prepared copolyester has better mechanical property, the elongation at break can reach more than 1000%, and the breaking strength can reach 25 MPa.
The invention is realized by the following scheme:
The first object of the invention is to provide a PBAT-based modified copolyester, which is obtained by introducing hydrophilic units into the PBAT copolyester for chemical modification; the hydrolytic property of the PBAT copolyester is increased by increasing the hydrophilicity of the PBAT copolyester, so that the PBAT copolyester is degraded in seawater;
The hydrophilic unit is ethylene glycol and/or polyethylene glycol;
the PBAT copolyester is obtained by carrying out esterification and polymerization reaction on terephthalic acid or derivatives thereof, adipic acid, 1, 4-butanediol, a heat stabilizer and a catalyst; the terephthalic acid or the derivative thereof is terephthalic acid or dimethyl terephthalate;
the chemical structural formula of the PBAT-based modified copolyester is as follows:
，
Wherein a is any integer from 2 to 68, m is any integer from 11 to 124, n is any integer from 14 to 132, and p+q is any integer from 1 to 172.
In one embodiment of the present invention, the ethylene glycol is selected from one or more of diethylene glycol, triethylene glycol, and tetraethylene glycol; the polyethylene glycol has a number average molecular weight of 600 g/mol-3000 g/mol.
In one embodiment of the invention, the content of the hydrophilic monomer is 5% -50% of the total mass of the PBAT-based modified copolyester.
In one embodiment of the invention, the PBAT-based modified copolyester is capable of achieving degradation in seawater; the degradation rate of the PBAT-based modified copolyester is regulated according to the content of the hydrophilic groups introduced; the higher the content of the hydrophilic groups is, the faster the degradation rate of the obtained PBAT-based modified copolyester is; at 37 ℃, the PBAT-based modified copolyester is degraded in a phosphate buffer salt solution containing lipase for 56 days, the weight loss is 18% -59%, and the weight loss of the PBAT copolyester under the same condition is only 3%. At 28 ℃, the PBAT-based modified copolyester is degraded in the east sea water containing lipase for 56 days, the weight loss is 7% -20%, and the PBAT copolyester under the same condition has no weight loss.
In one embodiment of the invention, the PBAT-based modified copolyester has a relatively high molecular weight and excellent mechanical properties; the number average molecular weight of the PBAT-based modified copolyester is more than 30 kg/mol, and the PBAT-based modified copolyester has good mechanical properties. The PBAT-based modified copolyester has high molecular weight and excellent mechanical properties. The breaking strength of the PBAT-based modified copolyester can reach 10-25 MPa; the elongation at break is greater than 1000%.
The second object of the invention is to provide a preparation method of the PBAT-based modified copolyester, which comprises the following steps: uniformly mixing terephthalic acid or a derivative thereof with adipic acid, 1, 4-butanediol, a hydrophilic monomer, a heat stabilizer and a catalyst, esterifying at first in an inert atmosphere, and then heating to perform vacuum condensation polymerization to obtain the PBAT-based modified copolyester; the terephthalic acid or the derivative thereof is terephthalic acid or dimethyl terephthalate.
According to the invention, the seawater degradation performance of the obtained PBAT-based modified copolyester is regulated in a larger range by regulating the content of the hydrophilic monomer in the copolyester.
In one embodiment of the present invention, the molar ratio of terephthalic acid or its derivative to adipic acid is 2:1 to 1:2.
In one embodiment of the present invention, the molar ratio of the sum of the moles of terephthalic acid or the derivative thereof and adipic acid to the moles of 1, 4-butanediol is 1:1.1 to 1.5; the esterification temperature is 180-220 ℃, preferably 180-205 ℃; the temperature of the condensation polymerization is 240-270 ℃.
In one embodiment of the invention, the catalyst is one or more of titanium, antimony and germanium catalysts, preferably tetrabutyl titanate, antimony trioxide and tetra-n-butoxygermane; the heat stabilizer is phosphate stabilizer, preferably triphenyl phosphate and/or triethyl phosphorylacetate.
In one embodiment of the invention, the catalyst is added in an amount of 0.02-0.5% of the total mass of the terephthalic acid or the derivative thereof and the adipic acid; the addition amount of the heat stabilizer is 0.05-1 per mill of the total mass of the terephthalic acid or the derivative thereof and the adipic acid.
In one embodiment of the invention, the gas in the inert atmosphere is nitrogen and/or argon.
The third object of the invention is to provide the application of the PBAT-based modified copolyester in the field of seawater degradation.
The PBAT-based modified copolyester has excellent mechanical properties and a relatively fast seawater degradation rate, and the seawater degradation rate can be regulated and controlled in a large range according to different contents of hydrophilic groups.
Compared with the prior art, the technical scheme of the invention has the following advantages:
The invention provides a PBAT-based modified copolyester and a preparation method thereof (a synthetic route diagram is shown in figure 1), hydrophilic monomers are introduced into a PBAT main chain, and the hydrophilicity of a polymer is improved, so that the PBAT-based modified copolyester with high degradation speed is obtained, and the PBAT-based modified copolyester has degradability in seawater, and solves the problem that the PBAT copolyester is difficult to degrade in seawater. The obtained PBAT-based modified copolyester with high degradation speed has excellent mechanical properties, the elongation at break can reach more than 1000%, the breaking strength can reach 25 MPa, and the popularization and application values are high.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. Wherein,
FIG. 1 is a synthetic route diagram of a PBAT based modified copolyester according to the present invention;
FIG. 2 is a volume exclusion chromatogram of the PBAT-based modified copolyester PBAT3EG-1 synthesized in example 2 of the present invention;
FIG. 3 is a volume exclusion chromatogram of the PBAT-based modified copolyester PBAT3EG-2 synthesized in example 3 of the present invention;
FIG. 4 is a volume exclusion chromatogram of the PBAT based modified copolyester PBAT4EG-1 synthesized in example 5 of the present invention;
FIG. 5 is a volume exclusion chromatogram of the PBAT-based modified copolyester PBAT-PEG 600 -1 synthesized in example 7 of the present invention;
FIG. 6 is a graph showing degradation of the quality of the PBAT-based modified copolyester PBAT3EG-2 of test example 1 over time in a phosphate buffer saline solution at 37℃under lipase-free and lipase-containing conditions according to the present invention;
FIG. 7 is a graph showing degradation of the quality of the PBAT-based modified copolyester PBAT3EG-2 of test example 2 over time at 37℃in east sea water, without and with lipase;
FIG. 8 is a graph showing degradation of the quality of the PBAT-based modified copolyester PBAT3EG-2 of test example 3 over time in the presence of lipase-free and lipase-containing conditions in east sea water at 28 ℃;
FIG. 9 is a graph showing degradation of the quality of the PBAT-based modified copolyester PBAT3EG-3 of test example 4 over time in a phosphate buffer saline solution at 37℃under conditions without and with lipase;
FIG. 10 is a graph showing the degradation of the quality of the PBAT-based modified copolyester PBAT3EG-3 of test example 5 according to the present invention over time in the absence of lipase and in the presence of lipase in the presence of the same in the sea water at 37℃east ocean;
FIG. 11 is a graph showing the degradation of the quality of the PBAT-based modified copolyester PBAT3EG-3 of test example 6 according to the present invention over time in 28℃east sea water, without and with lipase;
FIG. 12 is a graph showing degradation of the quality of the PBAT-based modified copolyester PBAT-PEG 600 -2 of test example 7 of the present invention over time in phosphate buffered saline at 37℃in the absence of lipase and in the presence of lipase;
FIG. 13 is a graph showing the degradation of the PBAT-based modified copolyester PBAT-PEG 600 -2 of test example 8 of the present invention over time at 37℃in east sea water, without and with lipase;
FIG. 14 is a graph showing the degradation of the PBAT-based modified copolyester PBAT-PEG 600 -2 of test example 9 according to the present invention over time in east ocean water at 28℃under conditions of no lipase and lipase;
FIG. 15 is a stress-strain plot (tensile rate: 20 mm/min, temperature: 16.0 ℃, humidity: 54.0%) of the PBAT-based modified copolyester PBAT3EG-2 of test example 10 according to the present invention;
FIG. 16 is a stress-strain plot (tensile rate: 20 mm/min, temperature: 16.0 ℃, humidity: 54.0%) of the PBAT-based modified copolyester PBAT-PEG 600 -1 of test example 11 of the present invention;
FIG. 17 is a graph showing the degradation profile of the quality of the PBAT copolyester of test example 12 of the present invention over time in phosphate buffered saline at 37℃under conditions without and with lipase; PBAT only loses 3% weight in phosphate buffered saline for 56 days;
FIG. 18 is a graph showing the degradation of the PBAT copolyester of test example 13 according to the present invention over time in east sea water at 28℃under conditions of no lipase and lipase; the PBAT copolyester has no weight loss in the east sea water.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
The CAS numbers for the organic reagents used in the present invention are shown below:
TABLE 1
In the following examples of the present invention, experiments were performed on degradation of copolyesters in phosphate buffered saline (PBS buffer) and east sea water, both of which are commercially available. Degradation experiments were divided into lipase-free and lipase-containing groups (lipase name: pseudomonas cepacia lipase, enzyme activity: 30.0X10 3 units per gram). The degradation experiments of the copolyester in phosphate buffered saline or east-ocean seawater at 37 ℃ were performed using the following methods: the copolyester sample is pressed into round small slices with the thickness of 0.2 mm, the round small slices with the thickness of about 5.0 mg are weighed and immersed into phosphate buffer salt solution or east sea water containing lipase (concentration: 1.00 mg/mL) with the concentration of about 0.5 mL, and a degradation experiment is carried out by shaking the table lightly. A control set of experiments was also provided, performed in phosphate buffered saline without lipase, with the other conditions unchanged. And taking out the sample when the sample reaches a preset number of days, leaching with distilled water, filtering, drying, and weighing the mass change by using an electronic balance. Furthermore, the solution was changed every three days. Degradation levels were evaluated according to the following formula: residual weight percent= (post-degradation mass/pre-degradation mass) ×100%, weight loss is 100% -residual weight percent.
Similarly, the environmental temperature is adjusted to 28 ℃, and the test is carried out by standing in the sea water of the east sea, so as to obtain the corresponding sea water degradation performance.
In the following examples of the invention, the tensile properties of the products were tested using an universal materials tester model Instron-5966. (draw rate: 20 mm/min, temperature: 16.0 ℃, humidity: 54.0%).
Example 1
In the embodiment, diethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT2EG-1:
Terephthalic acid (16.6 g), adipic acid (7.30 g), 1, 4-butanediol (14.9 g), diethylene glycol (7.5 g), tetrabutyl titanate (14 mg) and triphenyl phosphate (20 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is increased to 180 ℃ to react 1.5 h, then the temperature is increased to 200 ℃ to react 0.5 h, vacuum pumping and pressure reduction are carried out to be less than 100 Pa, the temperature is increased to 260 ℃, and the reaction is carried out for 3h, thus obtaining the PBAT-based modified copolyester PBAT2EG-1.
Example 2
In the embodiment, triethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT3EG-1:
dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (23.4 g), triethylene glycol (2.6 g), tetrabutyl titanate (7 mg) and triphenyl phosphate (10 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1.5 h, then the temperature is raised to 200 ℃ to react 0.5 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3h, so that the PBAT-based modified copolyester PBAT3EG-1 is obtained.
The volume exclusion chromatogram of the PBAT-based modified copolyester PBAT3EG-1 prepared in this example is shown in FIG. 2, and the number average molecular weight is found to be 36600 g/mol.
Example 3
In the embodiment, triethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT3EG-2:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (21.6 g), triethylene glycol (10.4 g), tetrabutyl titanate (14 mg) and triphenyl phosphate (14 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1.5 h, then the temperature is raised to 200 ℃ to react 0.5 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3.5 h, so that the PBAT-based modified copolyester PBAT3EG-2 is obtained.
The volume exclusion chromatogram of the PBAT-based modified copolyester PBAT3EG-2 prepared in this example is shown in FIG. 3, and the number average molecular weight was found to be 31400 g/mol.
Example 4
In the embodiment, triethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT3EG-3:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (19.8 g), triethylene glycol (20.8 g), tetrabutyl titanate (27 mg) and triphenyl phosphate (20 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 190 ℃ to react 1.5 h, then the temperature is raised to 200 ℃ to react 1 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 4h, thus obtaining the PBAT-based modified copolyester PBAT3EG-3 copolyester.
Example 5
In the embodiment, tetraethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT4EG-1:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (19.8 g), tetraethylene glycol (5.2 g), tetrabutyl titanate (15 mg) and triphenyl phosphate (15 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 195 ℃ to react 1.5h, then the temperature is raised to 200 ℃ to react 0.5 h, the vacuum is pumped and reduced to 100 Pa or lower, the temperature is raised to 260 ℃, and the reaction is 3 h, so that the PBAT-based modified copolyester PBAT4EG-1 is obtained.
The volume exclusion chromatogram of the PBAT-based modified copolyester PBAT4EG-1 prepared in this example is shown in FIG. 4, and the number average molecular weight was found to be 30100 g/mol.
Example 6
In the embodiment, tetraethylene glycol is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT4EG-2:
Dimethyl terephthalate (9.7 g), adipic acid (14.6 g), 1, 4-butanediol (14.9 g), tetraethylene glycol (7.56 g), antimony trioxide (15 mg) and triethyl phosphorylacetate (15 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1.5 h, then the temperature is raised to 200 ℃ to react 1h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3 h, so that the PBAT-based modified copolyester PBAT4EG-2 is obtained.
Example 7
In the embodiment, polyethylene glycol (PEG 600) with the number average molecular weight of 600 is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT-PEG 600 -1:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (19.8 g), polyethylene glycol (10.4 g) with the number average molecular weight of 600, tetrabutyl titanate (16 mg) and triphenyl phosphate (16 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1h, then the temperature is raised to 200 ℃ to react 1.5 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3h, thus obtaining the PBAT-based modified copolyester PBAT-PEG 600 -1.
The volume exclusion chromatogram of the PBAT-based modified copolyester PBAT-PEG 600 -1 prepared in this example is shown in FIG. 5, and the number average molecular weight was found to be 33900 g/mol.
Example 8
In the embodiment, polyethylene glycol (PEG 600) with the number average molecular weight of 600 is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT-PEG 600 -2:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (19.8 g), polyethylene glycol (20.8 g) with the number average molecular weight of 600, tetrabutyl titanate (16 mg) and triphenyl phosphate (16 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1h, then the temperature is raised to 200 ℃ to react 1.5 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3h, thus obtaining the PBAT-based modified copolyester PBAT-PEG 600 -2.
Example 9
In the embodiment, polyethylene glycol (PEG 2000) with the number average molecular weight of 2000 is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT-PEG 2000 -1:
Terephthalic acid (8.3 g), adipic acid (14.6 g), 1, 4-butanediol (14.9 g), polyethylene glycol (7.34 g) with the number average molecular weight of 2000, tetra-n-butoxygermane (17 mg) and triphenyl phosphate (17 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1h, then the temperature is raised to 200 ℃ to react 1.5 h, vacuumizing and decompressing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out 3h, thus obtaining the PBAT-based modified copolyester PBAT-PEG 2000 -1.
Example 10
In the embodiment, polyethylene glycol (PEG 3000) with the number average molecular weight of 3000 is introduced for condensation polymerization to synthesize PBAT-based modified copolyester PBAT-PEG 3000 -1:
Dimethyl terephthalate (19.4 g), adipic acid (7.3 g), 1, 4-butanediol (14.9 g), polyethylene glycol (7.34 g) with a number average molecular weight of 3000, tetrabutyl titanate (17 mg) and triphenyl phosphate (17 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 200 ℃ for reaction 1h and then raised to 220 ℃ for reaction 1.5 h, vacuumizing and depressurizing are carried out to 100 Pa or below, the temperature is raised to 270 ℃, and the reaction 3h is carried out, so that the PBAT-based modified copolyester PBAT-PEG 3000 -1 is obtained.
Test example 1
Degradation test of PBAT-based modified copolyester PBAT3EG-2 in phosphate buffer salt solution at 37 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-2 with time is shown in FIG. 6. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in phosphate buffer salt solution at 37 ℃, and the weight loss reaches 18% after degradation for 56 days. In addition, in the control group without lipase addition, the PBAT3EG-2 copolyester sample also had a weight loss of approximately 6.1% after 56 days.
Test example 2
Degradation test of PBAT-based modified copolyester PBAT3EG-2 in the east sea water at 37 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-2 with time is shown in FIG. 7. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in seawater at 37 ℃, and the weight loss reaches 4.9% after degradation for 28 days. In the control group without lipase addition, the PBAT-based modified copolyester PBAT3EG-2 sample also had a weight loss of 2% after 28 days.
Test example 3
And (3) degradation test of the PBAT-based modified copolyester PBAT3EG-2 in the east sea water at 28 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-2 with time is shown in FIG. 8. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in seawater at 28 ℃, and the weight loss reaches 7.2% after degradation for 56 days. In the control group without lipase addition, the PBAT-based modified copolyester PBAT3EG-2 sample also had a weight loss of approximately 3.5% after 56 days of degradation.
Test example 4
Degradation test of PBAT-based modified copolyester PBAT3EG-3 in phosphate buffer salt solution at 37 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-3 sample over time is shown in FIG. 9. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in phosphate buffer salt solution at 37 ℃, and the weight loss reaches 59% after degradation for 56 days. In the control group without lipase addition, copolyester PBAT3EG-3 also had a weight loss of approximately 15% after 56 days.
Test example 5
Degradation test of PBAT-based modified copolyester PBAT3EG-3 in the east sea water at 37 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-3 with time is shown in FIG. 10. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in the east sea water at 37 ℃, and the weight loss reaches 14% after degradation for 28 days. In the control group without lipase addition, the copolyester PBAT3EG-3 sample also had a weight loss of approximately 3.8% after 28 days.
Test example 6
And (3) degradation test of the PBAT-based modified copolyester PBAT3EG-3 in the east sea water at 28 ℃ under the conditions of no lipase and lipase.
The degradation curve graph of the degradation quality of the PBAT-based modified copolyester PBAT3EG-3 sample over time is shown in FIG. 11. The figure shows that the quality of the PBAT-based modified copolyester PBAT3EG-3 is rapidly reduced in seawater at 28 ℃ under the action of lipase, and the weight loss reaches 20% after degradation for 56 days. In addition, in the control group without lipase addition, the PBAT-based modified copolyester PBAT3EG-3 sample also had a weight loss of approximately 6.0% after degradation for 56 days.
Test example 7
Degradation test of PBAT-PEG 600 -2 copolyester in phosphate buffered saline at 37℃without lipase and with lipase.
The degradation profile of the quality of degradation of the PBAT-PEG 600 -2 copolyester over time is shown in figure 12. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in phosphate buffer salt solution at 37 ℃, and the weight loss reaches 22% after degradation for 56 days. In the control group without lipase addition, the PBAT-PEG 600 -3 copolyester sample also had a weight loss of approximately 4.8% after degradation for 56 days.
Test example 8
Degradation test of PBAT-PEG 600 -2 copolyester in east sea water at 37 ℃ without lipase and under lipase-containing conditions.
The degradation profile of the quality of degradation of the PBAT-PEG 600 -2 copolyester over time is shown in FIG. 13. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in seawater at 37 ℃, and the weight loss reaches 10% after degradation for 28 days. In addition, in the control group without lipase addition, there was a weight loss of approximately 2.8% after 28 days for the PBAT-PEG 600 -3 copolyester sample.
Test example 9
And (3) degradation test of the PBAT-based modified copolyester PBAT-PEG 600 -2 in the east sea water at 28 ℃ under the conditions of no lipase and lipase.
The degradation profile of the degradation quality of the PBAT-based modified copolyester PBAT-PEG 600 -2 over time is shown in FIG. 14. From the graph, the quality of the copolyester is rapidly reduced under the action of lipase in seawater at 28 ℃, and the weight loss reaches 12% after the degradation for 56 days. In addition, in the control group without lipase addition, the PBAT-based modified copolyester PBAT-PEG 600 -2 sample also had a weight loss of approximately 4.0% after degradation for 56 days.
Test example 10
Tensile test of the PBAT-based modified copolyester PBAT3 EG-2.
The PBAT-based modified copolyester PBAT3EG-2 prepared in example 3 was pressed into 0.2 mm thick sheets, cut into dumbbell-shaped bars, and tensile tested at a tensile rate of 20 mm/min, the stress-strain graph of the PBAT3EG-2 copolyester is shown in fig. 15, the young's modulus of the polymer was 32 MPa, the breaking strength was 25 MPa, and the elongation at break was more than 1000%, indicating that the polymer has excellent mechanical properties.
Test example 11
Tensile test of PBAT-based modified copolyester PBAT-PEG 600 -1.
The PBAT-based modified copolyester PBAT-PEG 600 -1 prepared in example 7 was pressed into 0.2mm thick sheets, cut into dumbbell-shaped bars, and subjected to tensile test at a tensile rate of 20 mm/min, the stress-strain curve of the PBAT-PEG 600 -1 copolyester is shown in fig. 16, the young's modulus of the polymer is 52 MPa, the breaking strength is 25 MPa, and the breaking elongation is greater than 1000%, indicating that the polymer has excellent mechanical properties.
Comparative example 1
The comparative example provides a preparation method of PBAT copolyester, which is synthesized by condensation polymerization of dimethyl terephthalate, adipic acid and 1, 4-butanediol:
Dimethyl terephthalate (19.4 g), adipic acid (14.6 g), 1, 4-butanediol (19.8 g), tetrabutyl titanate (16 mg) and triphenyl phosphate (16 mg) are added into a reaction bottle, nitrogen is introduced, the temperature is raised to 185 ℃ to react 1.5h, then the temperature is raised to 200 ℃ to react 0.5 h, vacuumizing and decompressing are carried out to 100 Pa or below, the temperature is raised to 260 ℃, and the reaction is carried out for 3 h, thus obtaining the PBAT copolyester.
Test example 12
Degradation test of PBAT copolyester in phosphate buffered saline at 37 ℃ without lipase and with lipase.
The degradation profile of the quality of PBAT copolyester degradation over time is shown in fig. 17. From the figure, the degradation speed of the PBAT copolyester in phosphate buffer saline solution containing lipase at 37 ℃ is extremely slow, and the weight loss after degradation for 56 days is only 3%. In addition, there was no weight loss of PBAT copolyester in the control group with no lipase addition.
Test example 13
Degradation test of PBAT copolyester in east sea water at 28 ℃ without lipase and with lipase.
The degradation profile of the quality of PBAT copolyester degradation over time is shown in fig. 18. From the figure, the PBAT copolyester has no weight loss in seawater containing lipase at 28 ℃.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The PBAT-based modified copolyester is characterized in that the PBAT-based modified copolyester is obtained by introducing hydrophilic units into the PBAT copolyester for chemical modification; the hydrolytic property of the PBAT copolyester is increased by increasing the hydrophilicity of the PBAT copolyester, so that the PBAT copolyester is degraded in seawater;
The hydrophilic unit is ethylene glycol and/or polyethylene glycol;
the PBAT copolyester is obtained by carrying out esterification and polymerization reaction on terephthalic acid or derivatives thereof, adipic acid, 1, 4-butanediol, a heat stabilizer and a catalyst; the terephthalic acid or the derivative thereof is terephthalic acid or dimethyl terephthalate;
the chemical structural formula of the PBAT-based modified copolyester is as follows:
，
Wherein a is any integer from 2 to 68, m is any integer from 11 to 124, n is any integer from 14 to 132, and p+q is any integer from 1 to 172.
2. The PBAT-based modified copolyester of claim 1, wherein the ethylene glycol is selected from one or more of diethylene glycol, triethylene glycol, and tetraethylene glycol; the polyethylene glycol has a number average molecular weight of 600 g/mol-3000 g/mol.
3. The PBAT-based modified copolyester of claim 1, wherein the content of the hydrophilic unit is 5% -50% of the total mass of the PBAT-based modified copolyester.
4. The PBAT-based modified copolyester of claim 1, wherein the PBAT-based modified copolyester is capable of undergoing degradation in seawater; the degradation rate of the PBAT-based modified copolyester is regulated according to the content of the hydrophilic groups introduced.
5. The PBAT-based modified copolyester of claim 1, wherein the PBAT-based modified copolyester has a number average molecular weight of greater than 30 kg/mol and good mechanical properties.
6. The preparation method of the PBAT-based modified copolyester is characterized by comprising the following steps of: uniformly mixing terephthalic acid or a derivative thereof with adipic acid, 1, 4-butanediol, a hydrophilic monomer, a heat stabilizer and a catalyst, esterifying at first in an inert atmosphere, and then heating to perform vacuum condensation polymerization to obtain the PBAT-based modified copolyester; the terephthalic acid or the derivative thereof is terephthalic acid or dimethyl terephthalate.
7. The method according to claim 6, wherein the molar ratio of terephthalic acid or a derivative thereof to adipic acid is 2:1 to 1:2.
8. The method according to claim 6, wherein the molar ratio of the sum of the moles of terephthalic acid or a derivative thereof and adipic acid to the moles of 1, 4-butanediol is 1:1.1 to 1.5; the esterification temperature is 180-220 ℃; the temperature of the condensation polymerization is 240-270 ℃.
9. The method of claim 6, wherein the catalyst is one or more of titanium, antimony and germanium catalysts; the heat stabilizer is triphenyl phosphate and/or triethyl phosphorylacetate.
10. The preparation method according to claim 6, wherein the catalyst is added in an amount of 0.02 to 0.5% by weight of the total mass of terephthalic acid or its derivative and adipic acid; the addition amount of the heat stabilizer is 0.05-1 per mill of the total mass of the terephthalic acid or the derivative thereof and the adipic acid.
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| CN115260542A (en) * | 2022-07-11 | 2022-11-01 | 湖北宜化降解新材料有限公司 | Preparation method of degradable polymer/starch masterbatch |
| CN117384365A (en) * | 2023-11-27 | 2024-01-12 | 陕西煤业化工技术研究院有限责任公司 | Degradable copolyester and preparation method and application thereof |
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| CN115124827A (en) * | 2022-07-11 | 2022-09-30 | 三峡大学 | Preparation method of degradable polymer/calcium carbonate master batch |
| CN115260542A (en) * | 2022-07-11 | 2022-11-01 | 湖北宜化降解新材料有限公司 | Preparation method of degradable polymer/starch masterbatch |
| CN117384365A (en) * | 2023-11-27 | 2024-01-12 | 陕西煤业化工技术研究院有限责任公司 | Degradable copolyester and preparation method and application thereof |
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