CN100551950C - A kind of preparation method of degradable polyester-amide copolymer - Google Patents
A kind of preparation method of degradable polyester-amide copolymer Download PDFInfo
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- CN100551950C CN100551950C CNB2005100205498A CN200510020549A CN100551950C CN 100551950 C CN100551950 C CN 100551950C CN B2005100205498 A CNB2005100205498 A CN B2005100205498A CN 200510020549 A CN200510020549 A CN 200510020549A CN 100551950 C CN100551950 C CN 100551950C
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- Prior art keywords
- amide copolymer
- polyester
- caprolactone
- omega
- reaction
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- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 230000009194 climbing Effects 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 14
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 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 3
- 239000000203 mixture Substances 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000007731 hot pressing Methods 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 description 10
- 235000010582 Pisum sativum Nutrition 0.000 description 9
- 240000004713 Pisum sativum Species 0.000 description 9
- 229920000120 polyethyl acrylate Polymers 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The present invention relates to a kind of degradable polyester-amide copolymer and simple and effective preparation method thereof.Be characterized in that with 6-caprolactone and omega-amino acid be reaction monomers; under catalyst action, generate degradable polyester-amide copolymer through melt polymerization; its polyreaction is that nitrogen protection is earlier 120～140 ℃ of reactions one hour; then be warming up to 160～180 ℃ and also keep reaction 1 hour; remove nitrogen then; in 10 minutes, be decompressed to 2.5kPa and be warmed up to 230～270 ℃ of reactions; discharging when rod climbing phenomenon appears in system; thereby obtain the polyester-amide copolymer multipolymer, reaction yield is 90.0%～98.1%.This polyester-amide copolymer viscosity (30 ℃, 0.5g dl
-1M-cresol solution in) at 0.51-1.23dlg
-1Between, its fusing point (Tm) is between 54-170 ℃, and the tensile strength of 1.00mm thickness, 6.00mm width hot pressing matrix is between 13-60MPa, between the elongation at break 21%-1200%, 1.0mm the thickness matrix is in PH=7.2 buffered soln, degraded was between 0.20wt%-12.50wt% in 100 days.When the content of ester bond in the polyester-amide copolymer during greater than 50% molar content, multipolymer can be dissolved in the chloroform solvent.
Description
The present invention relates to a kind of degradable polyester-amide copolymer and preparation method thereof, belong to the synthetic field of macromolecular material.Its product is mainly used in functional high molecule material, environment-friendly material and has the biological medical polymer material prospect.
Polyesteramide (PEAs) is a kind of novel biodegradable polymer, the existence of acid amides segment molecule interchain hydrogen bond makes PEAS material when molecular weight is low also have higher thermomechanical property and intensity, and material favorable biological degradability energy is given in aliphatic poly esteramides segmental existence simultaneously again.This performance of PEAs is with a wide range of applications it.Y.Tokiwa makes catalyzer with polycaprolactone (PCL) and polymeric amide PA-6, PA-66, PA-612, PA-11, PA-12 with Glacial acetic acid zinc, carries out the permutoid reaction of ester-acid amide key and obtain polyester-amide copolymer under high temperature, nitrogen protection.Along with the prolongation of permutoid reaction time of ester-acid amide key, the degree of randomness of polymkeric substance increases.The prepared polyesteramide unstable properties of this macromolecular reaction method, circulation ratio relatively poor (J Appl Polym Sci, 1979,24:1701-1711); Minnesota Mining and Manufacturing Company obtains the acid amides dibasic alcohol with oxyacetic acid or lactic acid and diamine reaction, itself and acyl chlorides is reacted to obtain polyester-amide copolymer then in solvent.The use of acyl chlorides and a large amount of solvents all has bigger negative impact to staff, plant and instrument and environment in building-up process.(the world technology research and development of improving one's methods, 2000,22, be to utilize oxyacetic acid, 1 1:66-71), 12-12 diamines, 6-caprolactone and hexanediamine are that raw material obtains two kinds of acid amides dibasic alcohol intermediates, further carry out the melt co-polycondensation reaction with diprotic acid again, by regulating the ratio of two kinds of acid amides dibasic alcohol, can obtain a series of performance differences, the polyester-amide copolymer that degradation speed is different, but reaction still needed through the intermediate stage; I.Goodman (European Polymer Journal, 1984,20:529-537.) to be reaction monomers do the catalyst anions copolymerization with sodium caprolactam(ate) generates polyester-amide copolymer: I.Arvanitoyannis (D.Angew Makrom Chem with 6-caprolactone and hexanolactam, 1994,222:111-123.) be that the reaction monomers melt polymerization obtains polyester-amide copolymer with hexanodioic acid, hexanediamine and 6-caprolactone, but the productive rate low (45-92%) of reaction.
The objective of the invention is provides a kind of simple effective method to prepare degradable polyester-amide copolymer at the deficiencies in the prior art.Be characterized in 6-caprolactone and omega-amino acid (carbochain segment length=6 or 11) being that the reaction monomers melt polymerization generates degradable polyester-amide copolymer, reaction process is simply effective, the productive rate height, reaction can quantitatively be carried out, and can adjust the structure and the performance of product to a great extent.
The objective of the invention is to adopt following measure to realize:
A kind of degradable polyester-amide copolymer is characterized in that the starting raw material recipe ingredient of degradable polyester-amide copolymer is (by the mole branch):
6-caprolactone 25-75
Omega-amino acid 75-25
Catalyzer (butyl (tetra) titanate or stannous octoate) 0.1～0.5wt% (6-caprolactone+omega-amino acid)
The preparation method of degradable polyester-amide copolymer
Polyreaction
With 6-caprolactone (ε-CL); omega-amino acid and catalyzer are added in the four-necked bottle; feed nitrogen protection, elevated temperature is earlier 120～140 ℃ of reactions one hour; then be warming up to 160～180 ℃ and also keep reaction 1 hour; remove nitrogen then, be decompressed to 2.5kPa in 10 minutes and be warmed up to 230～270 ℃ of reactions, discharging when rod climbing phenomenon appears in system; thereby obtain the PEAs multipolymer, its reaction formula is:
N=5 or 10
Reaction yield of the present invention is 90.0%～98.1%, the degradable polyester-amide copolymer thermoplastic elastomer of preparation, and different according to raw materials used and formula rate can obtain 54-170 ℃ of product fusing point (Tm); Anti-open test what 15 ℃ of room temperatures, humidity 50%, speed 200mm/min carried out, the tensile strength of 1.00mm thickness, 6.00mm width hot pressing matrix is at 13-60MPa, elongation at break 21%-1200%; In the buffered soln of 37 ℃ of PH=7.2,100 days degradable 0.10wt%-12.50wt% of 1.0mm thickness matrix; When the content of ester bond in the polyester-amide copolymer during greater than 50% molar content, multipolymer can be dissolved in the chloroform solvent.
The present invention has the following advantages:
1. reaction was finished by one step of melt polymerization, basically identical in the ratio of key-amido linkage and the reaction monomers in the polyesteramide ester of reaction yield height, generation, and method is simply effective.
2. polyester-amide copolymer well combines the degradation property of aliphatic polyester and the thermal characteristics and the mechanical property of fatty polyamide.
3. use 6-caprolactone to be reaction monomers,, can in very large range control the structure and the performance of product by regulating its kind and proportioning with different chain length omega-amino acid.
Below be embodiments of the invention.
Embodiment 1. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 10.06 (0.077mol) and about 0.4wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC) obtained
70/30Polyesteramide, reaction yield are 95.5%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.
The product index
Reaction yield is 95.5%
Ester/acid amides mol ratio: 1/0.42 viscosity (30 ℃, 0.5g dl
-1M-cresol solution in): 0.88 (dlg
-1)
Fusing point (Tm): 57.7 ℃ of degree of crystallinity: 17.7%
Tensile strength: 25.7MPa Young's modulus: 160.0MPa
Yield point strength: 6.7MPa extension at break: 1015.1%
Degradation speed: 15.6wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)
Be dissolvable in water in the chloroform solvent
Embodiment 2: the starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 35.52g (0.269mol) and about 0.5wt% stannous octoate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC) obtained
40/60Polyesteramide, reaction yield are 92.3%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.
The product index
Ester/acid amides mol ratio: 1/1.34 viscosity (30 ℃, 0.5g dl
-1M-cresol solution in): 0.83 (dl/g)
Fusing point (Tm): 102.9 ℃ of degree of crystallinity: 16.2%
Tensile strength: 43.1MPa Young's modulus: 309.0MPa
Yield point strength: 15.6MPa extension at break: 566.0%
Degradation speed: 8.9wt%/100D (in the buffered soln of 37 ℃ of PH=7.2)
Be not dissolved in the chloroform solvent
Embodiment 3: the starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 11-aminoundecanoic acid (AU) 24.00g (0.119mol), 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AU) obtained
60/40Polyesteramide, reaction yield are 94.7%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.Matrix thickness is about 1.00mm.
The product index
Ester/acid amides mol ratio: 1/0.68 viscosity (30 ℃, 0.5g dl
-1M-cresol solution in); 0.70 (dl/g)
Fusing point (Tm): 72.9 ℃ of degree of crystallinity: 21.3%
Tensile strength: 38.1MPa Young's modulus: 233.0MPa
Yield point strength: 11.6MPa extension at break: 180.0%
Degradation speed: 1.8wt%/100D
Be dissolvable in water in the chloroform solvent
Embodiment 4. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 11-hexosamine (AU) 83.91g (0.417mol) and about 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AU) obtained
30/70Polyesteramide, reaction yield are 91.0%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.
The product index
Ester/acid amides mol ratio: 1/2.35 viscosity (30 ℃, 0.5g dl
-1M-cresol solution in): 0.88 (dlg
-1)
Fusing point (Tm): 65.7 ℃, 155.3 ℃ degree of crystallinity: 24.3%
Tensile strength: 55.7MPa Young's modulus: 369.0MPa
Yield point strength: 21.7MPa extension at break: 46.1%
Degradation speed; 0.13wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)
Be not dissolved in the chloroform solvent
Embodiment 5. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 11.81g (0.0895mol), 11-hexosamine (AU) 18.03g (0.0895mol) and about 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC/AU) obtained
50/25/25Polyesteramide, reaction yield are 94.5%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.
The product index
Ester/acid amides mol ratio: 1/0.48 viscosity (30 ℃, 0.5gdl
-1M-cresol solution in): 0.85 (dlg
-1)
Fusing point (Tm): 77.7 ℃ of degree of crystallinity: 18.7%
Tensile strength: 43.7MPa Young's modulus: 281.0MPa
Yield point strength: 16.7MPa extension at break: 246.1%
Degradation speed: 3.56wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)
Be dissolvable in water in the chloroform solvent
Used starting material all are marketable material among the above embodiment.
Claims (1)
1. the preparation method of a degradable polyester-amide copolymer, it is characterized in that: with 6-caprolactone, omega-amino acid and catalyzer are added in the four-necked bottle, feed nitrogen protection, elevated temperature, earlier 120～140 ℃ of reactions one hour, then be warming up to 160～180 ℃ and also keep reaction 1 hour, remove nitrogen then, in 10 minutes, be decompressed to 2.5kPa and be warmed up to 230～270 ℃ of reactions, discharging when rod climbing phenomenon appears in system, thus polyester-amide copolymer obtained; Wherein, in the composition of raw materials, 6-caprolactone and omega-amino acid component count by molar, 6-caprolactone is 25-75 part, omega-amino acid is 75-25 part, catalyst levels accounts for 0.1～0.5% of above-mentioned 6-caprolactone and omega-amino acid total mass, and omega-amino acid is a kind of or 6-aminocaprolc acid in 6-aminocaprolc acid, the 11-aminoundecanoic acid and the mixture of 11-aminoundecanoic acid, and catalyzer is butyl (tetra) titanate or stannous octoate.
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| ES2558357T3 (en) * | 2011-06-23 | 2016-02-03 | Dsm Ip Assets B.V. | Micro- or nanoparticles comprising a biodegradable polyesteramide copolymer for use in the delivery of bioactive agents |
| US9873765B2 (en) | 2011-06-23 | 2018-01-23 | Dsm Ip Assets, B.V. | Biodegradable polyesteramide copolymers for drug delivery |
| EP2903592B1 (en) | 2012-10-02 | 2019-01-23 | DSM IP Assets B.V. | Drug delivery composition comprising proteins and biodegradable polyesteramides |
| US10538864B2 (en) | 2012-10-24 | 2020-01-21 | Dsm Ip Assets, B.V. | Fibers comprising polyesteramide copolymers for drug delivery |
| WO2016097297A1 (en) | 2014-12-18 | 2016-06-23 | Dsm Ip Assets B.V. | Drug delivery system for delivery of acid sensitive drugs |
| CN105482102B (en) * | 2015-12-07 | 2017-09-19 | 中北大学 | Semi-aromatic transparent polyamide and its synthetic method |
| CN105348520B (en) * | 2015-12-07 | 2017-09-19 | 中北大学 | Semiaromatic polyamide composition and its synthetic method |
| CN115537000A (en) * | 2021-06-29 | 2022-12-30 | 中石化南京化工研究院有限公司 | Biodegradable composite material and preparation method and application thereof |
| CN115612079A (en) * | 2022-12-15 | 2023-01-17 | 中国农业科学院农业环境与可持续发展研究所 | Caprolactam-doped polycaprolactone and preparation method thereof |
| CN116063673B (en) * | 2023-03-07 | 2023-07-21 | 苏州大学 | Polyamide elastomer and preparation method and application thereof |
| CN116535642A (en) * | 2023-05-30 | 2023-08-04 | 天津工业大学 | Synthesis method of bio-based degradable polyester amide |
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