CN1837259A - Degradable polyester-amide copolymer and its preparation process - Google Patents
Degradable polyester-amide copolymer and its preparation process Download PDFInfo
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- CN1837259A CN1837259A CN 200510020549 CN200510020549A CN1837259A CN 1837259 A CN1837259 A CN 1837259A CN 200510020549 CN200510020549 CN 200510020549 CN 200510020549 A CN200510020549 A CN 200510020549A CN 1837259 A CN1837259 A CN 1837259A
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- amide copolymer
- degradable polyester
- caprolactone
- amino acid
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Abstract
The invention discloses a decomposable polyesteramide copolymer and preparing method, which is characterized by the following: adapting epsilon-caprolactone and amino acid as reacting monomer to polymerize the decomposable polyesteramide copolymer under the action of catalyst; reacting for one hour at 120-140 deg.c protected by nitrogen; heating until 160-180 deg.c and keeping for a hour; removing nitrogen; reducing pressure to 2.5 kPa within ten min and reacting at 230-270 deg.c; discharging when the system appears climbing phenomenon; producing the polyesteramide copolymer with 0.51-1.23 dlg-1 (30 deg.c 0.51 gdl-1 m-cresol solution), 54-170 deg.c Tm, 1.00 mm thickness, 6.0 mm breadth, 13-60 Mpa stretching strength, 21-1200 percent cracking extensibility, 1.0 mm thichness in the 7.2 pH value buffer and 0.20 wt -12.50 wt percent for 100 days.
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, be that reaction monomers is made catalyst anions copolymerization generation polyester-amide copolymer with sodium caprolactam(ate) 20:529-537.) with 6-caprolactone and hexanolactam; I.Arvanitoyannis (D.Angew Makrom Chem, 1994, be that the reaction monomers melt polymerization obtains polyester-amide copolymer 222:111-123.) 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
The preparation method of catalyzer (butyl (tetra) titanate or stannous octoate) 0.1～0.5wt% (6-caprolactone+omega-amino acid) 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 ℃, 0.5gdl
-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 ℃, 0.5g dl
-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 (5)
1, 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 0.1～0.5wt% (6-caprolactone+omega-amino acid)
The degradable polyester-amide copolymer structural formula is
N=5 or 10.
2, a kind of degradable polyester-amide copolymer according to claim 1, its feature is 6-caprolactone and omega-amino acid in this reaction monomers, and omega-amino acid can be a kind of or 6-aminocaprolc acid in 6-aminocaprolc acid, the 11-aminoundecanoic acid and the mixture of 11-aminoundecanoic acid.
3, a kind of degradable polyester-amide copolymer according to claim 1 is characterized in that catalyzer is butyl (tetra) titanate or stannous octoate.
4, a kind of preparation method of degradable polyester-amide copolymer; it is characterized in that: with 6-caprolactone (ε-CL); 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.
5, according to the preparation method of claim 4 degradable polyester-amide copolymer, it is characterized in that using 6-caprolactone to be reaction monomers with different chain length omega-amino acid, by regulating its kind and proportioning, can in very large range control the structure and the performance of product.
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| CN103748139A (en) * | 2011-06-23 | 2014-04-23 | 帝斯曼知识产权资产管理有限公司 | Micro- or nanoparticles comprising a biodegradable polyesteramide copolymer for use in the delivery of bioactive agents |
| CN105348520A (en) * | 2015-12-07 | 2016-02-24 | 中北大学 | Semi-aromatic polyamide and synthesis method thereof |
| CN105482102A (en) * | 2015-12-07 | 2016-04-13 | 中北大学 | Semi-aromatic transparent polyamide and synthesis method thereof |
| US9789189B2 (en) | 2012-10-02 | 2017-10-17 | Dsm Ip Assets Bv | Drug delivery composition comprising proteins and biodegradable polyesteramides |
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| DE3482475D1 (en) * | 1983-12-27 | 1990-07-19 | Daicel Chem | POLYESTERAMID. |
| CN1256280A (en) * | 1998-12-09 | 2000-06-14 | 中国科学院成都有机化学研究所 | Biologically degradable polyester-polyamide copolymer and its preparation |
| CN1124304C (en) * | 1999-06-23 | 2003-10-15 | 中国科学院成都有机化学研究所 | Method for preparing biodegradable polyester-amide |
| CN1232564C (en) * | 2002-11-07 | 2005-12-21 | 上海交通大学 | Superbranched polyamide-ester and its preparation method |
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| US9873764B2 (en) | 2011-06-23 | 2018-01-23 | Dsm Ip Assets, B.V. | Particles comprising polyesteramide copolymers for drug delivery |
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| JP2017075320A (en) * | 2011-06-23 | 2017-04-20 | ディーエスエム アイピー アセッツ ビー．ブイ． | Novel biodegradable polyesteramide copolymers for drug delivery |
| JP2014522886A (en) * | 2011-06-23 | 2014-09-08 | ディーエスエム アイピー アセッツ ビー．ブイ． | Novel biodegradable polyesteramide copolymers for drug delivery |
| CN103748139A (en) * | 2011-06-23 | 2014-04-23 | 帝斯曼知识产权资产管理有限公司 | Micro- or nanoparticles comprising a biodegradable polyesteramide copolymer for use in the delivery of bioactive agents |
| US9963549B2 (en) | 2011-06-23 | 2018-05-08 | Dsm Ip Assets, B.V. | Biodegradable polyesteramide copolymers for drug delivery |
| US9789189B2 (en) | 2012-10-02 | 2017-10-17 | Dsm Ip Assets Bv | 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 |
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| CN105482102B (en) * | 2015-12-07 | 2017-09-19 | 中北大学 | Semi-aromatic transparent polyamide and its synthetic method |
| CN105482102A (en) * | 2015-12-07 | 2016-04-13 | 中北大学 | Semi-aromatic transparent polyamide and synthesis method thereof |
| CN105348520A (en) * | 2015-12-07 | 2016-02-24 | 中北大学 | Semi-aromatic polyamide and synthesis method thereof |
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| 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 |
| CN116063673A (en) * | 2023-03-07 | 2023-05-05 | 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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