CN100513456C - Alternative polyesteramide capable of biological degradating and its preparing method - Google Patents
Alternative polyesteramide capable of biological degradating and its preparing method Download PDFInfo
- Publication number
- CN100513456C CN100513456C CNB2007100279081A CN200710027908A CN100513456C CN 100513456 C CN100513456 C CN 100513456C CN B2007100279081 A CNB2007100279081 A CN B2007100279081A CN 200710027908 A CN200710027908 A CN 200710027908A CN 100513456 C CN100513456 C CN 100513456C
- Authority
- CN
- China
- Prior art keywords
- polyesteramide
- biological
- degradating
- alternative
- diester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a biodegradable alternating polyesteramide and its preparation method. The molecular formula of the alternating polyesteramide as shown in the figure: n=3-25, m=20-40, the polyesteramide can completely degraded in simulated saline with 70deg.C and pH 12, and its molecular weight is 20000-150000. In the preparation, anhydride is first alcoholyzed with PEG to produce diester-dicarboxylic compounds, then reacts with SOC12 to produce diester-dicarboxylic chloride, and the degradable polyesteramide copolymer can be produced through the interfacial polycondensation of diester-dicarboxylic chloride and diamine. The polyesteramide prepared through the present invention has good hydrophilic, mechanical and degradation properties, and the speed of biodegradation is adjustable, so it can be used in environmentally-friendly materials and biomedical materials.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material, relate to a kind of alternative polyesteramide capable of biological degradating and preparation method thereof, its product is mainly used in environment-friendly material and bio-medical material.
Background technology
Polyesteramide is a kind of novel biodegradable polymer, the existence of acid amides segment intermolecular hydrogen bonding makes polyesteramide material when molecular weight is low also have higher thermomechanical property and intensity, and material favorable biological degradability energy is given in the existence of ester bond simultaneously again.This performance of polyesteramide is with a wide range of applications it.
Y.Tokiwa makes catalyzer with polycaprolactone and polymeric amide PA-6, PA-6, PA-612, PA-612, PA-11, PA-12 with Glacial acetic acid zinc, carries out the permutoid reaction of ester-acid amide key and obtain the polyesteramide multipolymer 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 permutoid reaction unstable properties of the ester-acid amide key that this macromolecular reaction method makes, poor reproducibility.
Chinese invention patent 99115200.X, 00112700.4 and 00112699.7 reports the preparation method of biodegradable block polyesteramide of plasticity and multipolymer thereof respectively, all can realize degraded at acid-base condition and coenocorrelation, but these polymerization processs all adopt the high temperature polymerization method, be difficult to overcome side reactions such as ester-acid amide exchange, and in the preparation process of polyesteramide, all use virose diisocyanate cpd, make its range of application obtain restriction.
A kind of polyesteramide multipolymer that contains lactic acid of Chinese invention patent 9812899.7 report, but these polyesteramides is synthetic all comparatively complicated, and be difficult to overcome the generation of side reaction such as transesterify, cause these polymkeric substance or multipolymer darker colour-change to occur.Han Mo Jeong etc. is published in (1998 on the Polymer magazine, 39 (2): 459-465) " elastomeric phase structure of polyamide thermoplastic ester and character " paper reports that a kind of poly adipate succinic acid ester of carboxy blocking and hexanodioic acid are raw material, with tetramethylene sulfone is solvent, at 200 ℃ and 1, the hexamethylene-diisocyanate reaction, prepare the polyesteramide elastomerics, but such polyesteramide can not biological degradation.Liu Xiaobo is published in (2000 on the world technology research and development magazine, 22 (1): 66-71) " progress of Biodegradable polyester amides and multipolymer thereof " paper report utilizes oxyacetic acid, 1,12-12 carbon alkyl diamines, 6-caprolactone and hexanediamine obtain two kinds of acid amides dibasic alcohol monomers, further carry out the melt co-polycondensation reaction again with diprotic acid, by regulating the ratio of two kinds of acid amides dibasic alcohol, can obtain a series of performance differences, the different polyesteramide multipolymer of degradation speed, but reaction needed still through the intermediate stage.
U.S. Pat P4343931 and US P4529793 have reported hydroxyethanoic acid and aliphatic diamine reaction synthesizing amide dibasic alcohol, have studied biological degradability and absorptivity; But the derivative of having studied acid amides dibasic alcohol and binary acid prepares biodegradable and polyesteramide bio-absorbable, characterize in detail its structure and performance, and preparation can be used for the medical surgical operating sutures and is applied to biodegradable artificial bone fracture internal fixing device system.But the polyesteramide of these structures is hemicrystalline high molecular polymers, biodegradation rate is difficult to regulate and control, to such an extent as to bring other side effect, and the higher reason of cost also makes this base polymer can't be extensive use of environment protection material field.
Polyoxyethylene glycol (PEG) is linear water soluble polyether polymer, toxicity, immunogenicity and antigenicity are all very low, though be non-biodegradable material, when molecular weight Mw＜10000, easily be excreted, can be used in vivo by U.S. food and drug administration (FDA) approval.PEG molecular chain kindliness is good, and the molecular chain height stretches in the aqueous solution, and hydrodynamic volume is big, is that a kind of good material surface wetting ability is modified reagent.Consider the wetting ability of PEG excellence and to the adjustable degradation characteristic of polymkeric substance, the present invention is by introducing the PEG component in the dicarboxylic acid monomer, again with diamine prepared in reaction polyesteramide polymkeric substance, mechanical property that it is excellent and regulatable degradation characteristic can be applied at environment-friendly material and bio-medical material.Bibliographical information is not seen in the preparation of this base polymer as yet.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of alternately polyesteramide and preparation method thereof with good hydrophilicity, biodegradability and machine-shaping characteristic is provided.
Purpose of the present invention is achieved through the following technical solutions:
A kind of alternative polyesteramide capable of biological degradating, molecular formula is:
Wherein: n is 3-25, and m is 20-40;
R
1For
---(CH
2)
2---or---CH=CH---;
R
2For
-(CH
2)
4-,-(CH
2)
6-,-(CH
2)
8-,-(CH
2)
10-or-(CH
2)
12-.
This polyesteramide can be degraded in 70 ℃, pH are 12 simulation physiological saline fully, and its molecular weight is 20000-150000, and second-order transition temperature is at-10 ℃ to 34 ℃, and contact angle is 31.3 °～73.2 °.The tensile strength of the film of making is at 15-37MPa, and elongation at break is at 300%-800%.
The preparation method of alternative polyesteramide capable of biological degradating comprises the steps and processing condition:
(1) acid anhydrides and PEG are joined in the chloroform by two-to-one molar weight, under 1-5 polyoxyethylene glycol molar equivalent pyridine existence condition, under 40-85 ℃ of temperature, reacted 6-24 hour, obtain the diester dicarboxylic acid compound; Polyoxyethylene glycol (PEG) molecular weight is preferably 150-2000.
(2) under 0-25 ℃ of temperature condition, in the diester dicarboxylic acid compound, drip the SOCl of 2-10 molar equivalent
2After, reacted 1-10 hour, then at room temperature, hydrogenchloride in the high vacuum removal system and form waste gas of sulfur dioxide and superfluous SOCl
2, make diester diacid chloride compound;
(3) diester diacid chloride compound is dissolved in organic solvent after, mix with the alkaline aqueous solution of equimolar amount diamine, under 0-25 ℃ of temperature condition, by interfacial polycondensation reaction 5-120 minute, the gained crude product was after purifying, vacuum-drying makes alternative polyesteramide capable of biological degradating.Organic solvent is halogenated alkane solvent or alkyl aromatic hydrocarbon solvent.The halogenated alkane solvent comprises chloroform, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, methylene bromide, methenyl bromide or methyl iodide; Alkyl aromatics comprises benzene,toluene,xylene, o-Xylol or trimethylbenzene.
The principle of the invention: acid anhydrides and PEG alcoholysis make the diester dicarboxylic acid compound, with SOCl
2Reaction makes the diester diacid chloride, and diester diacid chloride and diamine obtain degradable poly carboxylic acid amide esters multipolymer by interfacial polycondensation.This reaction process is simply effective, and reaction can quantitatively be carried out, and can adjust the structure and the performance of product to a great extent.Its reaction formula is:
With respect to prior art, the present invention has following advantage:
(1) select for use acid anhydrides, diamine and polyoxyethylene glycol (PEG) to prepare the polyesteramide polymkeric substance for composition, product has good hydrophilicity, biological degradability and machine-shaping characteristic.
(2) adopting polyoxyethylene glycol PEG is the copolymerization component, can regulate the degradation rate and the surperficial hydrophilic and hydrophobic of product easily, also helps and biologically active substance, sticks as protein, cell etc., and application prospect is more arranged in organizational project.
(3) raw material sources are abundant, cost is low and product price is lower than biodegradable poly(lactic acid), polycaprolactone, owing to have preferable performance and lower price, are easy to apply, and have remarkable economic efficiency and social benefit.
(4) adopt interface fasculation method to prepare polyesteramide, have quick, easy, characteristics of high efficiency, and can overcome the generation of side reactions such as ester-ester bond permutoid reaction, ester-acid amide key permutoid reaction.
Description of drawings
Fig. 1 is the alternately hydrogen spectrogram of polyesteramide of embodiment 1 preparation.
Embodiment
The invention will be further described below in conjunction with embodiment.After research and testing, the contriver develops many successful examples, enumerates the part specific embodiment below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Under 20mmol pyridine existence condition, the 40mmol Tetra hydro Phthalic anhydride is joined 150mL contain in the 20mmol PEG400 chloroformic solution, in 40 ℃ of reactions 6 hours, obtain the diester dicarboxylic acid compound, under 10 ℃, drip the SOCl of 120mmol to this compound
2After, keep this thermotonus 1 hour, and at room temperature use 3 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in the 200mL tetracol phenixin, 1 of 40mmol, the 6-hexanediamine is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 0 ℃ two solution are mixed stirring 5 minutes, must replace polyesteramide, its hydrogen spectrum as shown in Figure 1 behind the purifying, 7.50-7.78ppm among the figure (a) ownership is the chemical shift of hydrogen on the phenyl ring, 7.43ppm (e) ownership is the chemical shift of hydrogen on the amido linkage, 4.41ppm (b) ownership is the chemical shift of the continuous methylene radical hydrogen of ester bond, illustrate and have the polyoxyethylene glycol unit in the polymkeric substance, 3.57-3.73ppm (c, d, f) ownership is the chemical shift of methylene radical hydrogen on continuous methylene radical hydrogen of amido linkage and the polyethylene glycol backbone, 1.36,1.65 (g) ownership is 1, the chemical shift of residue methylene radical hydrogen in the 6 hexanediamine unit, the ownership of above-mentioned chemical shift conforms to the structure of subject polymer, illustrates successfully to have synthesized this polymkeric substance.This polyesteramide molecular weight 27000, productive rate 53%, contact angle are 48.2 °, and second-order transition temperature is at 19.4 ℃, and the tensile strength of film is at 23MPa, and elongation at break is 420%.Complete degradation time is 59 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 2
Under 20mmol pyridine existence condition, the 40mmol Succinic anhydried is joined 150mL contain in the 20mmol PEG600 chloroformic solution, in 60 ℃ of reactions 6 hours, obtain the diester dicarboxylic acid compound, under 10 ℃, drip the SOCl of 160mmol to this compound
2After, keep this thermotonus 3 hours, and at room temperature use 3 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in the 200mL methylene dichloride, 1 of 40mmol, the 6-hexanediamine is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 0 ℃ two solution is mixed stirring 10 minutes, after products therefrom is purified, molecular weight 35000, productive rate 56%, contact angle are 51.2 °, and second-order transition temperature is at-3.4 ℃, the tensile strength of film is at 18MPa, and elongation at break is 550%.Complete degradation time is 46 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 3
Under 40mmol pyridine existence condition, the 40mmol Tetra hydro Phthalic anhydride is joined 150mL contain in the 20mmolPEG150 chloroformic solution, in 60 ℃ of reactions 8 hours, obtain the diester dicarboxylic acid compound, under 0 ℃, drip the SOCl of 40mmol to this compound
2After, keep this thermotonus 3 hours, and at room temperature use 3 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in the 200mL methenyl bromide, 1 of 40mmol, the 8-octamethylenediamine is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 10 ℃ two solution are mixed stirring 15 minutes, the purified back of products therefrom molecular weight 29000, productive rate 52%, contact angle is 54.2o, second-order transition temperature is at-1.6 ℃, and the tensile strength of film is at 21MPa, and elongation at break is 480%.Complete degradation time is 52 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 4
Under 60mmol pyridine existence condition, the 40mmol Tetra hydro Phthalic anhydride is joined 150mL contain in the 20mmol PEG600 chloroformic solution, in 60 ℃ of reactions 8 hours, obtain the diester dicarboxylic acid compound, under 0 ℃, drip the SOCl of 160mmol to this compound
2After, keep this thermotonus 4 hours, and at room temperature use 2 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in the 200mL chloroform, the mphenylenediamine of 40mmol is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 5 ℃ two solution are mixed stirring 15 minutes, the purified back of products therefrom molecular weight 63000, productive rate 68%, contact angle are 64.2 °, and second-order transition temperature is at 31.3 ℃, the tensile strength of film is at 35MPa, and elongation at break is 390%.Complete degradation time is 71 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 5
Under 20mmol pyridine existence condition, the 40mmol maleic anhydride is joined 150mL contain in the 20mmol PEG800 chloroformic solution, in 60 ℃ of reactions 10 hours, obtain the diester dicarboxylic acid compound, under 25 ℃, drip the SOCl of 160mmol to this compound
2After, keep this thermotonus 8 hours, and at room temperature use 2 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in 200mL toluene, the Ursol D of 40mmol is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 25 ℃ two solution are mixed stirring 30 minutes, the purified back of products therefrom molecular weight 71000, productive rate 73%, contact angle are 68.7 °, and second-order transition temperature is at 24.8 ℃, the tensile strength of film is at 27MPa, and elongation at break is 460%.Complete degradation time is 63 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 6
Under 20mmol pyridine existence condition, 40mmol fourth dicarboxylic acid anhydride is joined 150mL contain in the 20mmol PEG1500 chloroformic solution, in 60 ℃ of reactions 12 hours, obtain the diester dicarboxylic acid compound, under 0 ℃, drip the SOCl of 200mmol to this compound
2After, keep this thermotonus 7 hours, and at room temperature use 3 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in 200mL dimethylbenzene, 1 of 40mmol, the 10-decamethylene diamine is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 10 ℃ two solution are mixed stirring 40 minutes, the purified back of products therefrom molecular weight 54000, productive rate 75%, contact angle is 56.2 °, second-order transition temperature is at 27.3 ℃, and the tensile strength of film is at 38MPa, and elongation at break is 450%.Complete degradation time is 52 hours in the simulation physiological saline of 70 ℃ of pH=12.
Embodiment 7
Under 100mmol pyridine existence condition, the 40mmol Tetra hydro Phthalic anhydride is joined 150mL contain 20mmol
In the PEG2000 chloroformic solution,, obtain the diester dicarboxylic acid compound, under 10 ℃, drip the SOCl of 200mmol to this compound in 85 ℃ of reactions 24 hours
2After, keep this thermotonus 10 hours, and at room temperature use 2 hours hydrogenchloride and form waste gas of sulfur dioxide and superfluous SOCl in the high vacuum removal system
2, obtain diester diacid chloride compound.The diester diacid chloride of 40mmol is dissolved in the 200mL methylene bromide, 4 of 40mmol, 4 '-sulfobenzide diamines is dissolved in the aqueous solution that 200mL contains 80mmol NaOH, in 15 ℃ two solution are mixed stirring 120 minutes, the purified back of products therefrom molecular weight 79000, productive rate 73%, contact angle is 73.2 °, second-order transition temperature is at 35.4 ℃, and the tensile strength of film is at 45MPa, and elongation at break is 410%.Complete degradation time is 62 hours in the simulation physiological saline of 70 ℃ of pH=12.
Application Example: the 5 polyesteramide polymkeric substance that restrain by embodiment 5 gained are dissolved in chloroform, make 10% polyesteramide solution, adding particle diameter then is NaCl particle 10 grams of 100-300 μ m, back injection mould molding stirs, with the forming composition volatilization back demoulding naturally at normal temperatures, in vacuum drying oven, vacuumized again 24 hours, to remove chloroform remaining in the forming composition, forming composition was inserted in the redistilled water 72 hours, changed a water therebetween in per 6 hours, at room temperature dry 24 hours subsequently, vacuum-drying 48 hours more at last made a kind of tissue engineering bracket of high porosity.Support was soaked in the 20mL deionized water 24 hours in 25 ℃, the water-intake rate of support is 35%; In 37 ℃ support being soaked in pH is 7.4 phosphate buffer soln, and 48 hours after poppet quality are 74% of its original quality.Table 1 is the physicals control case table of polyesteramide tissue engineering bracket material of the present invention and poly(lactic acid) tissue engineering bracket.With the tissue engineering bracket ratio that is processed by poly(lactic acid) in the prior art, polyesteramide density of the present invention is by 0.099g/cm
3Bring up to 0.168g/cm
3, porosity brings up to 93.4% by 88.0%, and compressive strength is brought up to 1.76MPa by 0.95MPa.
Table 1
| Title material | Density (g/cm 3) | Porosity (%) | Compressive strength (MPa) | |
| Poly(lactic acid) | 0.099 | 88.0 | 0.95 | |
| Polyesteramide | 0.168 | 93.4 | 1.76 |
Claims (6)
1, a kind of alternative polyesteramide capable of biological degradating is characterized in that, alternately the molecular formula of polyesteramide is:
Wherein: n is 3-25, and m is 20-40;
R
1For
R
2For
-(CH
2)
4-,-(CH
2)
6-,-(CH
2)
8-,-(CH
2)
10-or-(CH
2)
12-.
2, alternative polyesteramide capable of biological degradating according to claim 1, it is characterized in that: this polyesteramide can be degraded in 70 ℃, pH are 12 simulation physiological saline fully, its molecular weight is 20000-150000, second-order transition temperature is at-10 ℃ to 34 ℃, and contact angle is 31.3 °～73.2 °.
3, the preparation method of the described alternative polyesteramide capable of biological degradating of claim 1 is characterized in that comprising the steps and processing condition:
(1) acid anhydrides and PEG are joined in the chloroform by two-to-one molar weight, under 1-5 polyoxyethylene glycol molar equivalent pyridine existence condition, under 40-85 ℃ of temperature, reacted 6-24 hour, obtain the diester dicarboxylic acid compound;
(2) under 0-25 ℃ of temperature condition, in the diester dicarboxylic acid compound, drip the SOCl of 2-10 molar equivalent
2After, reacted 1-10 hour, then at room temperature, hydrogenchloride in the high vacuum removal system and form waste gas of sulfur dioxide and superfluous SOCl
2, make diester diacid chloride compound;
(3) diester diacid chloride compound is dissolved in organic solvent after, mix with the alkaline aqueous solution of equimolar amount diamine, under 0-25 ℃ of temperature condition, by interfacial polycondensation reaction 5-120 minute, the gained crude product was after purifying, vacuum-drying makes alternative polyesteramide capable of biological degradating.
4, the preparation method of alternative polyesteramide capable of biological degradating according to claim 3 is characterized in that described PEG molecular weight is 150-2000.
5, the preparation method of alternative polyesteramide capable of biological degradating according to claim 3, the organic solvent that it is characterized in that described step (3) is halogenated alkane solvent or alkyl aromatic hydrocarbon solvent.
6, the preparation method of alternative polyesteramide capable of biological degradating according to claim 5 is characterized in that described halogenated alkane solvent comprises chloroform, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, methylene bromide, methenyl bromide or methyl iodide; Described alkyl aromatics comprises benzene,toluene,xylene, o-Xylol or trimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100279081A CN100513456C (en) | 2007-04-30 | 2007-04-30 | Alternative polyesteramide capable of biological degradating and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100279081A CN100513456C (en) | 2007-04-30 | 2007-04-30 | Alternative polyesteramide capable of biological degradating and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101070382A CN101070382A (en) | 2007-11-14 |
| CN100513456C true CN100513456C (en) | 2009-07-15 |
Family
ID=38897808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100279081A Expired - Fee Related CN100513456C (en) | 2007-04-30 | 2007-04-30 | Alternative polyesteramide capable of biological degradating and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100513456C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875802A (en) * | 2012-10-11 | 2013-01-16 | 南昌博生复合材料有限公司 | High-impact and heat-resistant copolymer and preparation method thereof |
| CN108102090A (en) * | 2016-11-24 | 2018-06-01 | 上海杰事杰新材料(集团)股份有限公司 | Ultra-toughness heat-stabilised poly amide resin and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835391B2 (en) * | 1999-09-30 | 2004-12-28 | Chienna B.V. | Poly (ether ester amide) and poly (ether ester urethane) copolymers |
-
2007
- 2007-04-30 CN CNB2007100279081A patent/CN100513456C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835391B2 (en) * | 1999-09-30 | 2004-12-28 | Chienna B.V. | Poly (ether ester amide) and poly (ether ester urethane) copolymers |
Non-Patent Citations (2)
| Title |
|---|
| Interfacial Polymerization or the Preparation of RegularlyAlternating Polyesteramides. J.L.R.WILLIAMS,J.M.CARLSON,and G.A.REYNOLDS.Die Makromolekulare Chemie,Vol.65 No.1. 2004 |
| Interfacial Polymerization or the Preparation of RegularlyAlternating Polyesteramides. J.L.R.WILLIAMS,J.M.CARLSON,and G.A.REYNOLDS.Die Makromolekulare Chemie,Vol.65 No.1. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101070382A (en) | 2007-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Winnacker et al. | Poly (ester amide) s: recent insights into synthesis, stability and biomedical applications | |
| Deng et al. | Synthesis and characterization of biodegradable poly (ester amide) s with pendant amine functional groups and in vitro cellular response | |
| Pang et al. | Synthesis, characterization and biodegradation of functionalized amino acid-based poly (ester amide) s | |
| US20140066587A1 (en) | Novel Biodegradable Elastomeric Scaffold for Tissue Engineering and Light Scattering Fingerprinting Methods for Testing the Same | |
| Bei et al. | Polycaprolactone–poly (ethylene‐glycol) block copolymer. IV: Biodegradation behavior in vitro and in vivo | |
| Gyawali et al. | Citric-acid-derived photo-cross-linked biodegradable elastomers | |
| CN103113579B (en) | Polyglutamic acid derivative as well as hydrogel and preparation method of polyglutamic acid derivative | |
| CN100513456C (en) | Alternative polyesteramide capable of biological degradating and its preparing method | |
| CN103159956A (en) | Aromatic-aliphatic biodegradable graft polymer | |
| CN101076362A (en) | Biodegradable and bioresorbable material for medical use | |
| JP5258189B2 (en) | Flexible biodegradable polymer | |
| Lee et al. | Synthesis and degradation behaviors of PEO/PL/PEO tri-block copolymers | |
| JP2008222768A (en) | Branched biodegradable polyester and method for producing the same | |
| US7196127B2 (en) | Biodegradable polyesteramide and preparation method | |
| JP7173259B1 (en) | Biodegradable resin composition, molded article and biodegradation method | |
| US20230181793A1 (en) | Functionalized poly(glycerol sebacate)s and uses thereof | |
| Guo et al. | Design strategies and applications of citrate-based biodegradable elastomeric polymers | |
| CN102898656A (en) | Method for preparing a chitosan / aliphatic polyester amphiphilic graft copolymer | |
| CN1176978C (en) | Degradable chemically crosslinked aquagel and its prepn | |
| CN1418901A (en) | Carboxy polylactic acid contained composition and preparation process thereof | |
| CN110559478A (en) | Preparation method of amino acid-based polyester ammonia electrostatic spinning nanofiber tissue engineering skin scaffold | |
| Katz et al. | Synthetic biomaterials | |
| JP2023072094A (en) | Biodegradable resin composition, and molded body | |
| Bianco et al. | Biocompatible α-aminoacids based aliphatic polyamides | |
| WO2023219145A1 (en) | Improvement of vitrimer by polyrotaxane addition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090715 Termination date: 20170430 |