CN117164833A - PBS copolyester capable of being rapidly degraded in water prepared from diester monomer containing three-membered ring and preparation method thereof - Google Patents
PBS copolyester capable of being rapidly degraded in water prepared from diester monomer containing three-membered ring and preparation method thereof Download PDFInfo
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- CN117164833A CN117164833A CN202311086736.0A CN202311086736A CN117164833A CN 117164833 A CN117164833 A CN 117164833A CN 202311086736 A CN202311086736 A CN 202311086736A CN 117164833 A CN117164833 A CN 117164833A
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- pyrrolidone
- cyclohexane
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 title abstract description 13
- 150000005690 diesters Chemical class 0.000 title abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 57
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 32
- FJRTVLWHONLTLA-UHFFFAOYSA-N methyl 5-oxopyrrolidine-3-carboxylate Chemical compound COC(=O)C1CNC(=O)C1 FJRTVLWHONLTLA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- 238000006731 degradation reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000001384 succinic acid Substances 0.000 claims abstract 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 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract 2
- 229960005137 succinic acid Drugs 0.000 claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- -1 (methyl pyrrolidone-4-carboxylate) butylene succinate repeat Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of high polymer material synthesis, and in particular relates to a method for preparing modified PBS copolyester by using a three-membered ring monomer, which is prepared by condensation polymerization of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 1, 4-butanediol and 1, 4-succinic acid serving as raw materials and tetrabutyl titanate serving as a catalyst under the protection of nitrogen at high temperature and high vacuum degree and under the condition of no solvent x BS y A copolyester. The invention has the advantages that the diester monomer synthesized from renewable resources is utilized, the raw material sources are wide, the reaction conditions are mild, the synthesis process is easy to operate, the prepared copolyester has adjustable performance, excellent thermal performance and good thermal stability, the possibility of industrial production is provided, the hydrolysis speed of PBS can be improved, and the environmental requirement of PBS degradation is reduced.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, relates to PBS (poly-styrene) copolymer capable of being rapidly hydrolyzed by using a monomer containing a three-membered ring and a preparation method thereof, and in particular relates to PBS copolyester capable of being rapidly hydrolyzed by using a monomer containing a three-membered ring, 1, 4-butanediol and 1, 4-succinic acid and a preparation method thereof.
Background
Poly (butylene succinate) (PBS) is a novel degradable polyester material, has the advantages of excellent mechanical property, good thermal stability and the like, is one of the environment-friendly materials which has the highest potential to replace the traditional high polymer, and is mainly applied to the fields of packaging materials, tableware, biomedical appliances and the like. However, it is highly hydrophobic and requires harsh conditions for degradation, such as in the presence of specific enzymes or microorganisms. It is difficult to degrade under natural conditions in PBS, resulting in serious white contamination of the PBS plastic. Conventionally, various methods have been employed to enhance the in-water degradation properties of PBS. Firstly, developing a new degradable polyester material to replace PBS; secondly, copolymerizing a hydrophilic monomer and PBS; and thirdly, adopting hydrophilic polymer or hydrophilic auxiliary agent to blend with PBS. There are a number of problems: if the new raw materials are high in cost, the modified PBS material is poor in thermal and mechanical properties, and the raw materials are still from non-renewable petrochemical byproducts and the like.
How to further improve the slow degradation problem of the PBS material in water under natural conditions by utilizing green raw materials under the condition of not affecting the thermal performance and mechanical properties of the PBS polyester is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a method for preparing modified PBS copolyester by using a diester monomer containing a three-membered ring, and the preparation method has the advantages of simple synthesis process, easy operation, high yield, environmental protection and easy industrialized popularization.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention provides a PBS copolyester capable of being rapidly degraded in water, which comprises a butanedioic acid ester repeating unit shown in a formula (a) and an N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butanedioic acid ester repeating unit shown in a formula (b),
the chemical name is: poly (butylene succinate-co-N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate
The PBS copolyester has the number average molecular weight not lower than 10000g/mol;
the degradation rate of the rapidly water-degradable PBS copolyester in 100 days of water is not lower than 30%.
Further, based on 100% of the rapidly water-degradable PBS copolyester, wherein the N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate repeating unit molar ratio is 5% -40%; the balance is butanediyl succinate repeating units.
Further, based on 100% of the rapidly water-degradable PBS copolyester, wherein the N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate repeating unit molar ratio is 20% -30%; the balance is butanediyl succinate repeating units.
In a second aspect, the present invention provides a process for preparing rapidly water-degradable PBS copolyesters from tri-cyclic diester monomers, said copolymers being obtained by condensation polymerization of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 1, 4-butanediol and 1, 4-butanedioic acid under solvent-free conditions.
Further, the preparation method of the PBS copolyester capable of being rapidly degraded in water comprises the following steps:
and (3) putting N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol, and 1, 4-succinic acid into a closed reactor, adding a catalyst, and sequentially carrying out transesterification, pre-polycondensation and polycondensation to obtain the PBS copolyester capable of being degraded in water rapidly.
Further, the molar ratio of the acid to the alcohol of the 1, 4-succinic acid, the N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and the 1, 4-butanediol is 1:1.2-3, more preferably a molar ratio of 1:1.5.
further, the catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.05-0.55 percent of the total feeding molar amount of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 1, 4-butanediol and 1, 4-succinic acid.
Further, the temperature of the transesterification reaction is 180-230 ℃, and the transesterification reaction time is 5-10 h.
Further, the polycondensation reaction is carried out under the vacuum degree of less than or equal to 100Pa, the polycondensation reaction temperature is 220-250 ℃, and the polycondensation reaction time is 2-10 h.
The beneficial effects of the invention are as follows:
1) In the invention, the PBS polyester is modified by using the renewable monomer, and the prepared polyester has good thermal stability and can reduce the dependence on petroleum resources;
2) The copolyester synthesis method is environment-friendly, simple in synthesis process, easy to operate, high in synthesis yield and capable of realizing large-scale production;
3) The copolyester material provided by the invention has adjustable performance, the PBS copolyester can be quickly degraded by adding the diester monomer, the defects of strong hydrophobicity and slow hydrolysis of the PBS are overcome, and the hydrolysis rate can be adjusted by adjusting the contents of 1, 4-succinic acid and N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-methyl carboxylate).
4) The N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) has a three-membered ring structure, the synthetic raw material is derived from biomass, and belongs to renewable resources, and the pyrrolidone ring has high hydrophilicity, and is subjected to copolymerization modification with PBS, so that the thermal performance and mechanical property of PBS polyester are not affected, the defect of difficult hydrolysis of the PBS polyester can be overcome, and the severe requirement of PBS degradation on the environment can be reduced.
Drawings
FIG. 1 is a DSC melting curve of example 1;
FIG. 2 is a DSC melting curve of example 2;
FIG. 3 is a plot of residual mass after degradation versus time for example 1;
fig. 4 is a plot of residual mass after degradation versus time for example 2.
Detailed Description
The following examples are given for the purpose of illustration only and are not to be construed as limiting the scope of the invention, as many insubstantial adaptations and modifications of the invention are within the scope of the invention as would be apparent to one of ordinary skill in the art.
In the examples which follow, all starting materials are essentially obtained commercially or are prepared by methods conventional in the art, unless otherwise specified.
In the following examples, the thermal transition analysis was carried out using a Q2000 type differential scanning calorimeter from TA company at a temperature rising rate of 10 ℃/min under a nitrogen atmosphere, and the temperature was in the range of-70 to 280 ℃.
In the following examples, the sample was cut into 5X 1mm sheets by compression molding, the sheets were placed in a glass bottle containing 15mL of deionized water, and the glass bottle was placed in a shaker at room temperature for 100 days to examine its water degradation properties.
In the examples, the rapidly water degradable PBS copolyesters are of chemical name: poly (butylene butyrate-co-N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene butyrate), abbreviated as PBC x BS y B, C, and S represent respectively 1, 4-butanediol, N, N '-trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-succinic acid, x and y are N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-succinic acid in a molar ratio of 100 in the copolyester; PBC as in example 1 20 BS 80 Representing that the molar ratio of PBC units in the PBS copolyester is 20%; the BS unit accounts for 80%.
Example 1
PBC 20 BS 80 Preparation of copolyester:
1) From diester monomers N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol, 1, 4-butanePreparation of PBC by condensation polymerization of diacid 20 BS 80 Copolyester, alkyd mole ratio 1.5:1, a step of;
2) Weighing 0.2mol of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 0.8mol of 1, 4-succinic acid and 1.5mol of 1, 4-butanediol according to the molar ratio of the initially designed alkyd, placing the mixture into a round bottom flask with good air tightness, dropwise adding 0.01mol of tetrabutyl titanate catalyst, and setting the transesterification temperature to 200 ℃ for reaction for 6 hours under the nitrogen atmosphere;
3) The vacuum degree is regulated to 60Pa, the temperature is increased to 220 ℃, and the polycondensation reaction is carried out for 6 hours to obtain the copolyester.
Example 2
PBC 30 BS 70 Preparation of copolyester:
1) Preparation of PBC by condensation polymerization of diester monomers N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol, 1, 4-butanedioic acid 30 BS 70 Copolyester, alkyd mole ratio 1.5:1, a step of;
2) Weighing 0.3mol of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 0.7mol of 1, 4-succinic acid and 1.5mol of 1, 4-butanediol according to the molar ratio of the initially designed alkyd, placing the mixture into a round bottom flask with good air tightness, dropwise adding 0.01mol of tetrabutyl titanate catalyst, and setting the transesterification temperature to 200 ℃ for reaction for 6 hours under the nitrogen atmosphere;
3) The vacuum degree is regulated to 60Pa, the temperature is increased to 220 ℃, and the polycondensation reaction is carried out for 6 hours to obtain the copolyester.
Test example 1
PBC 20 BS 80 Copolyester DSC test:
1) Weighing 5-10mg of the copolyester prepared in the example 1, and placing the copolyester in a differential scanning calorimeter to test a melting curve;
2) Setting a program of heating-isothermal-cooling-isothermal-heating, wherein the temperature test range is-70-280 ℃, and the temperature rise rates are all 10 ℃/min, so as to obtain a melting curve graph.
FIG. 1 shows PBC 20 BS 80 DSC melting curve of copolyester, glass transition temperature of the copolyester is observed from the graph(T g ) At-16.2℃with PBS T g Is-30 ℃. PBC (physical broadcast channel) 20 BS 80 T of the copolyester g Above the PBS.
Test example 2
PBC 30 BS 70 Copolyester DSC test:
1) Weighing 5-10mg of the copolyester prepared in the example 2, and placing the copolyester in a differential scanning calorimeter to test a melting curve;
2) Setting a program of heating-isothermal-cooling-isothermal-heating, wherein the temperature test range is-70-280 ℃, and the temperature rise rates are all 10 ℃/min, so as to obtain a melting curve graph.
FIG. 2 shows PBC 30 BS 70 The DSC melting curve of the copolyester, from which the glass transition temperature (T g ) PBS T at-3.2 ℃ g Is-30 ℃. PBC (physical broadcast channel) 30 BS 70 T of the copolyester g Above the PBS.
Test example 3
PBC 20 BS 80 Copolyester water degradation performance test:
1) Sample PBC 20 BS 80 Cutting the copolyester into sheets with the thickness of 5 multiplied by 1mm through compression molding, and placing the sheets into a glass bottle filled with 15mL of deionized water for water degradation test;
2) The glass bottle was placed in a shaker at room temperature and shaken for 100 days, the sheet was taken out at intervals to be dried, and the mass was weighed and the mass reduction ratio was recorded.
FIG. 3 shows PBC 20 BS 80 From the time-dependent change curve of the residual quality after the degradation of the copolyester, the PBS is stable without obvious quality degradation after 100 days of water degradation, which shows that the PBS has strong hydrophobicity. Whereas PBC 20 BS 80 The copolyester rapidly drops in quality along with degradation, and after 100 days, the quality remains 35%, so that the quick hydrolysis characteristic is shown.
Test example 4
PBC 30 BS 70 Copolyester water degradation performance test:
1) Sample PBC 30 BS 70 Copolyester passing through a diePressing and forming a sheet material cut into 5 multiplied by 1mm, and placing the sheet material into a glass bottle filled with 15mL of deionized water for water degradation test;
2) The glass bottle was placed in a shaker at room temperature and shaken for 100 days, the sheet was taken out at intervals to be dried, and the mass was weighed and the mass reduction ratio was recorded.
FIG. 4 shows PBC 30 BS 70 The residual mass change curve of the copolyester after degradation with time shows that the PBS is stable and has no obvious mass drop after 100 days of water degradation, thus indicating that the PBS has strong hydrophobicity. Whereas PBC 30 BS 70 The quality of the copolyester is rapidly reduced along with degradation, and after 100 days, the quality is 29 percent, so that the copolyester has the characteristic of rapid water degradation. With increasing N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) content, the hydrolysis rate increases.
While the foregoing description of the embodiments of the present invention has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the invention, but rather, it is intended to cover all modifications or variations within the scope of the invention as defined by the claims of the present invention.
Claims (10)
1. A PBS copolyester capable of being rapidly hydrolyzed is characterized by comprising a butanedioic acid ester repeating unit shown in a formula (a) and an N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butanedioic acid ester repeating unit shown in a formula (b),
the chemical name is: poly (butylene succinate-co-N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate);
the PBS copolyester has the number average molecular weight not lower than 10000g/mol;
the degradation rate of the rapidly water-degradable PBS copolyester in 100 days of water is not lower than 30%.
2. The rapidly hydrolyzable PBS copolyester of claim 1, wherein the N, N '-trans-1, 4-cyclohexane-bis (methyl pyrrolidone-4-carboxylate) butylene succinate repeat unit mole ratio is 5% to 40% based on the sum of N, N' -trans-1, 4-cyclohexane-bis (methyl pyrrolidone-4-carboxylate) butylene succinate repeat unit mole numbers in the rapidly water-degradable PBS copolyester taken as 100%; the balance is butanediyl succinate repeating units.
3. The rapidly hydrolyzable PBS copolyester of claim 2, wherein the mole ratio of N, N '-trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate repeat units is 20% to 30% based on the sum of the moles of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) butylene succinate repeat units in the rapidly water-degradable PBS copolyester taken as 100%; the balance is butanediyl succinate repeating units.
4. A process for the preparation of a rapidly water-degradable PBS copolyester as claimed in any one of claims 1 to 3, characterised in that the copolymer is obtained by condensation polymerisation of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 1, 4-butanediol and 1, 4-butanedioic acid in the absence of a solvent.
5. The method of manufacturing according to claim 4, comprising the steps of:
and (3) putting N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol, and 1, 4-succinic acid into a closed reactor, adding a catalyst, and sequentially carrying out transesterification, pre-polycondensation and polycondensation to obtain the PBS copolyester capable of being degraded in water rapidly.
6. The method according to claim 5, wherein the molar ratio of acid to alcohol of 1, 4-succinic acid, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol is 1:1.2-3.
7. The method according to claim 6, wherein the molar ratio of acid to alcohol of 1, 4-succinic acid, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester) and 1, 4-butanediol is 1:1.5.
8. the preparation method according to claim 5, wherein the catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.05-0.55% of the total addition molar amount of N, N' -trans-1, 4-cyclohexane-bis (pyrrolidone-4-carboxylic acid methyl ester), 1, 4-butanediol and 1, 4-succinic acid.
9. The method according to claim 5, wherein the transesterification reaction is carried out at a temperature of 180 to 230℃for a period of 5 to 10 hours.
10. The method according to claim 5, wherein the polycondensation is carried out under a vacuum of 100Pa or less, the polycondensation temperature is 220 to 250 ℃, and the polycondensation time is 2 to 10 hours.
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| CN202311086736.0A CN117164833A (en) | 2023-08-28 | 2023-08-28 | PBS copolyester capable of being rapidly degraded in water prepared from diester monomer containing three-membered ring and preparation method thereof |
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| CN202311086736.0A CN117164833A (en) | 2023-08-28 | 2023-08-28 | PBS copolyester capable of being rapidly degraded in water prepared from diester monomer containing three-membered ring and preparation method thereof |
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- 2023-08-28 CN CN202311086736.0A patent/CN117164833A/en active Pending
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