CN1396193A - Biodegradable ternary copolymer of polycarbonate, polyester and polyether and its preparing process - Google Patents
Biodegradable ternary copolymer of polycarbonate, polyester and polyether and its preparing process Download PDFInfo
- Publication number
- CN1396193A CN1396193A CN 01122588 CN01122588A CN1396193A CN 1396193 A CN1396193 A CN 1396193A CN 01122588 CN01122588 CN 01122588 CN 01122588 A CN01122588 A CN 01122588A CN 1396193 A CN1396193 A CN 1396193A
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- CN
- China
- Prior art keywords
- polycarbonate
- polyester
- peg
- glycol
- polyethers
- 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.)
- Granted
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 10
- 229920000515 polycarbonate Polymers 0.000 title claims description 11
- 239000004417 polycarbonate Substances 0.000 title claims description 11
- 229920000728 polyester Polymers 0.000 title claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract 2
- 229920006027 ternary co-polymer Polymers 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 229920001897 terpolymer Polymers 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229920001427 mPEG Polymers 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 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 description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HJBWJAPEBGSQPR-UHFFFAOYSA-N DMCA Natural products COC1=CC=C(C=CC(O)=O)C=C1OC HJBWJAPEBGSQPR-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 210000000578 peripheral nerve Anatomy 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 210000000626 ureter Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A biodegradable ternary copolymer, polycarbonate-polyester-polyether, is prepared through preparing cyclocarbonate from diethyl carbonate and diol by catalytic ester exchange, and reacting on epsilon-hexalactone and polyethanediol PEG at 110-170 deg.C for 12-72 hr in vacuum under action of catalyst. Its advantages are high biodegradability with adjustable degradating speed and high mechanical performance.
Description
Technical field
The present invention relates to aliphatic polycarbonate, relate in particular to a kind of biological degradability polycarbonate/polyester/polyethers terpolymer and preparation method.
Background technology
Aliphatic polyester is the absorbable and degradable type polymer that a big class has good biocompatibility as poly-glycollide, polylactide, poly-epsilon-caprolactone and multipolymer thereof, be widely used in medicine controlled releasing and organizational project, wherein poly-(lactide/glycolides) (PLGA) ratified the synthesising biological degraded type macromolecular material of use in vivo by FDA.Introducing carbonic acid ester bond in main polymer chain is a kind of effective ways that improve polyester biomaterial mechanical mechanics property.Aliphatic polycarbonate has good elasticity and film forming properties, but degradation rate is relatively slow, and the multipolymer of itself and glycollide, rac-Lactide, 6-caprolactone etc. makes with several different methods such as positively charged ion, negatively charged ion, polycoordination, enzyme-catalyzed polymerizations.Have in clinic trial, as the copolymer p (TMC-GA) of trimethylene carbonate and glycollide as the medical degradable suture.
PEG is linear water soluble polyether polymer, and toxicity, immunogenicity and antigenicity are all very low, though be non-biodegradable material, easily is excluded out externally when molecular weight MW＜10000, is used in vivo by the 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.PEG and rac-Lactide segmented copolymer PLEG particularly are widely used aspect the controlled release of polypeptide protein at medicine controlled releasing.
Consider polycarbonate good elasticity and film-forming properties, the physical strength that poly-epsilon-caprolactone is good and both are degradation characteristic slowly, it is the 3rd copolymerization component that the present invention adopts PEG, preparation carbonic ether/6-caprolactone/PEG terpolymer, mechanical property that it is excellent and suitable vivo degradation characteristic can particularly be applied in the reparation of soft tissue such as peripheral nerve, oesophagus, ureter, tendon etc. in organizational project.Bibliographical information is not seen in the preparation of this based terpolymers and application as yet.
Summary of the invention
The purpose of this invention is to provide a kind of polycarbonate/polyester/polyethers terpolymer and preparation method thereof with excellent biological compatibility, biodegradability and machine-shaping characteristic.Its molecular formula is:
PCL-CA-PEG
Wherein:
R
1＝H，CH
3 R
2＝H，CH
3
l＝1～200，m＝1～100，n＝5～250
The preparation method is: diethyl carbonate and glycol are made cyclic carbonate monomer CA with the sodium Metal 99.5 catalytic transesterification, and another comonomer 6-caprolactone, polyoxyethylene glycol PEG handle through dehydration and purification.Cyclic carbonate and 6-caprolactone, PEG are mixed with 1: 0.25～4: 0.25～2, are initiator with the stannous octoate, and 140～170 ℃ of following polymerizations 12～72 hours, the gained crude product was after separating purification, and vacuum-drying is preserved.
Advantage of the present invention:
1) selecting aliphatic acid ester carbonate, 6-caprolactone and polyoxyethylene glycol PEG for use is that composition prepares terpolymer, and product has excellent biological compatibility, biodegradability and machine-shaping characteristic.
2) adopting polyoxyethylene glycol PEG is copolymer composition, can regulate the degradation rate and the surperficial hydrophilic and hydrophobic of product easily, helps and biologically active substance, and as protein, cell etc. stick, and application prospect is more arranged in organizational project.
Embodiment
Be described in further detail below in conjunction with embodiment:
Above-mentioned glycol is: 1, and ammediol, 2-methyl isophthalic acid, ammediol, 2, said polyoxyethylene glycol PEG molecular weight is 200～20000, also can be Alpha-hydroxy-ω-methoxy poly (ethylene glycol) MPEG, molecular weight is 350～10000.
Embodiment 1
With diethyl carbonate and 2,2-dimethyl-1,3 propylene glycol is made cyclic carbonate monomer DMCA with the sodium Metal 99.5 catalytic transesterification.Monomer DMCA: CL: PEG (6000)=1: 4: 2 (mol ratio) 20 gram is placed polymerizing pipe, add stannous octoate petroleum ether solution (0.05g/ml, 2ml), drain solvent after, in 170 ℃ of following polymerase 17s 2 hours.The purified back of products therefrom molecular weight is about 30,000, productive rate 85%.
Embodiment 2
With diethyl carbonate and 1, ammediol is made cyclic carbonate monomer CA with the sodium Metal 99.5 catalytic transesterification.Monomer CA: CL: PEG (20000)=1: 0.25: 0.25 (mol ratio) 20 gram is placed polymerizing pipe, add stannous octoate petroleum ether solution (0.05g/ml, 2ml), drain solvent after, in 140 ℃ of following polymerizations 24 hours.The products therefrom molecular weight is about 20,000, and productive rate 80% has good snappiness and film-forming properties.Embodiment 3
With diethyl carbonate and 2-methyl isophthalic acid, 3 propylene glycol are made cyclic carbonate monomer MCA with the sodium Metal 99.5 catalytic transesterification.Monomer M CA: CL: MPEG (5000)=1: 2: 1 (mol ratio) 20 gram is placed polymerizing pipe, add stannous octoate petroleum ether solution (0.05g/ml, 2ml), drain solvent after, in 160 ℃ of following polyase 13s 6 hours.The products therefrom molecular weight is about 2.5 ten thousand, productive rate 85%.
Claims (4)
1. biological degradability polycarbonate/polyester/polyethers terpolymer, it is characterized in that: its molecular formula is:
PCL-CA-PEG is wherein: R
1=H, CH
3R
2=H, CH
3L=1～200, m=1～100, n=5～250
2. the preparation method of biological degradability polycarbonate/polyester/polyethers terpolymer, it is characterized in that: diethyl carbonate and glycol are made cyclic carbonate monomer CA with the sodium Metal 99.5 catalytic transesterification, another comonomer 6-caprolactone, polyoxyethylene glycol PEG handle through dehydration and purification, cyclic carbonate and 6-caprolactone, PEG are mixed with 1: 0.25～4: 0.25～2, with sad industry tin is initiator, 140～170 ℃ of following polymerizations 12～72 hours, the gained crude product is after purifying, vacuum-drying is preserved.
3. the preparation method of a kind of biological degradability polycarbonate/polyester according to claim 2/polyethers terpolymer is characterized in that said glycol is: 1,3 propylene glycol, 2-methyl isophthalic acid, 3 propylene glycol, 2,2-dimethyl-1,3 propylene glycol.
4. according to the preparation method of claim 2 or 3 described a kind of biological degradability polycarbonate/polyester/polyethers terpolymers, it is characterized in that said polyoxyethylene glycol PEG molecular weight is: 200～20000, also can be Alpha-hydroxy-ω-methoxy poly (ethylene glycol) MPEG, molecular weight is 350～10000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011225882A CN1164642C (en) | 2001-07-13 | 2001-07-13 | Biodegradable ternary copolymer of polycarbonate, polyester and polyether and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011225882A CN1164642C (en) | 2001-07-13 | 2001-07-13 | Biodegradable ternary copolymer of polycarbonate, polyester and polyether and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1396193A true CN1396193A (en) | 2003-02-12 |
| CN1164642C CN1164642C (en) | 2004-09-01 |
Family
ID=4664815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011225882A Expired - Fee Related CN1164642C (en) | 2001-07-13 | 2001-07-13 | Biodegradable ternary copolymer of polycarbonate, polyester and polyether and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1164642C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199879A (en) * | 2011-03-17 | 2011-09-28 | 无锡百和织造股份有限公司 | Acid-proof nylon hook-and-loop fastener and its manufacture method |
| CN109810246A (en) * | 2018-12-26 | 2019-05-28 | 深圳光华伟业股份有限公司 | A kind of low temperature polycaprolactone preparation method that fusing point is controllable |
| CN110305324A (en) * | 2014-05-07 | 2019-10-08 | 旭化成株式会社 | Water system composition polycarbonate/polyoxyethylene block copolymer and water system composition comprising it |
-
2001
- 2001-07-13 CN CNB011225882A patent/CN1164642C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199879A (en) * | 2011-03-17 | 2011-09-28 | 无锡百和织造股份有限公司 | Acid-proof nylon hook-and-loop fastener and its manufacture method |
| CN110305324A (en) * | 2014-05-07 | 2019-10-08 | 旭化成株式会社 | Water system composition polycarbonate/polyoxyethylene block copolymer and water system composition comprising it |
| CN110305324B (en) * | 2014-05-07 | 2022-01-28 | 旭化成株式会社 | Polycarbonate/polyoxyethylene block copolymer for aqueous composition, and aqueous composition containing same |
| CN109810246A (en) * | 2018-12-26 | 2019-05-28 | 深圳光华伟业股份有限公司 | A kind of low temperature polycaprolactone preparation method that fusing point is controllable |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1164642C (en) | 2004-09-01 |
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