CN1146466A - Synthetic method for biodegradability polyester material - Google Patents

Synthetic method for biodegradability polyester material Download PDF

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Publication number
CN1146466A
CN1146466A CN 96117591 CN96117591A CN1146466A CN 1146466 A CN1146466 A CN 1146466A CN 96117591 CN96117591 CN 96117591 CN 96117591 A CN96117591 A CN 96117591A CN 1146466 A CN1146466 A CN 1146466A
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China
Prior art keywords
lanthanon
monomer
polyester material
synthetic method
lncl
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Chinese (zh)
Inventor
邓先模
袁明龙
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Chengdu Institute of Organic Chemistry of CAS
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Chengdu Institute of Organic Chemistry of CAS
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Priority to CN 96117591 priority Critical patent/CN1146466A/en
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Abstract

The present invention relates to a method for synthesizing biodegradable polyester material. Said invented biodegradable polyester material is made up by using caprolactone, lactide and diglycolide, etc. as monomer, and making them by the process of homopolymerization or copolymerization or copolymerization by adding polyether. Its catalyst is alkyl rare earth compound or allyl rare earth compound, and the mole ratio of monomer/catalyst is 50-5000. Under the protection of inert gas the polymerization reaction is implemented at 0-200 deg.C for 10 sec.-24 hr. The obtained product is high in molecular weight, and possesses good biodegradability and biocompatibility, so that it is an excellent biomedical material, and can be used in daily life.

Description

The synthetic method of biodegradability polyester material
The present invention relates to the synthetic method of macromolecular material, particularly have the synthetic method of the polyester macromolecular material of biological degradability.
Along with Biomedical Development, urgent especially to the demand of biomedical material.Simultaneously, polymkeric substance is widely used in daily life, and " white pollution " also becomes the ecological problem that needs to be resolved hurrily.Thereby the macromolecular material of synthesizing biological degradable will have important practical value.The macromolecular material with excellent biodegradability and biocompatibility of generally acknowledging mainly is poly-epsilon-caprolactone, poly-D at present, the homopolymerization or the multipolymer of L-lactic acid, polyglycolic acid etc.These polymkeric substance can be obtained by the corresponding lactone ring-opening polymerization.
In recent years, lactone ring opening polymerization has been carried out a large amount of research both at home and abroad, especially negatively charged ion and positively charged ion ring-opening polymerization are studied early, cationic initiator (as the stannous octoate) effect that wherein with the pink salt is representative is better, but pink salt has certain toxicity, and this class material application on biomedicine is restricted.What study morely at present is polycoordination, especially active coordination ring-opening polymerization, (Polym.Bull such as Ph.Teyssie, 1989,22,475.Macromolecules, 1991,24,3207, Macromolecules, 1992,25,4242-4248.Polymer.Volume 35 Number, 23 1994.J.polymer Science:Part A, V.32,2099-2110,1994) studied (Et 3-p) Al (OR) P(1≤P≤3) to the katalysis of lactone ring opening polymerization, and proves living polymerization.U.S. Pat 5028667 is used Y (OiPr) 3Alkoxy rare-earth compound for catalysis lactone open loop living polymerizations such as (three yttrium isopropoxides).And be catalyzer with the alkoxy rare-earth compound, prepared polymericular weight is lower.This patent (US 5028667) is not specifically studied though to mention available alkyl rare earth compound be catalyzer.
The object of the present invention is to provide a kind of synthetic method for preparing the high-molecular weight Biodegradable material, it can not only realize the homopolymerization or the copolymerization of lactone, and can prepare the multipolymer of lactone and polyethers.
The object of the present invention is achieved like this: with 6-caprolactone, D, and L-rac-Lactide, glycollide, D, one or more in L-3-methyl-glycollide are monomer, with LnR 3Type or LiLnR 4Type alkyl rare earth compound is a catalyzer, can also use (C 3H 5) 2LnCl 5Mg 2(TMED) 2, (C 4H 7) 2LnCl 5Mg 2(TMED) 2, (C 4H 7) 2LnCl 5Mg 2(THF) 4The allyl group rare earth compounding is a catalyzer, Ln wherein is that Sc (scandium), Y (yttrium) or lanthanon are a kind of of 57～No. 71 elements, R is one or both in phenyl, substituted-phenyl, allyl group, substituted allyl, cyclooctatetraene base, the phenylacetylene base, TMED is a Tetramethyl Ethylene Diamine, and THF is a tetrahydrofuran (THF).In monomer/catalyst (mol ratio) is 50～5000; temperature is 0～200 ℃, and mass polymerization is carried out in reaction 10 second～8 hour under the condition of protection of inert gas; also can add aromatic hydrocarbon solvent such as benzene, toluene etc., polar solvent such as tetrahydrofuran (THF), dioxane, CH 2Cl 2, CHCl 3Deng and ether solvents such as non-polar phenyl ether, two methyl-phenoxides, making the concentration (weight ratio) of monomer in solvent is 5%～50%, temperature is 0～200 ℃, solution polymerization is carried out in inert gas protection reaction 5 minutes～24 hours down.
Also can add polyethers and 6-caprolactone, D, L-rac-Lactide, glycollide, D, one or more in L-3-methyl-glycollide carry out copolymerization.
When carrying out copolyreaction, all comonomers can be added simultaneously, also sectional adds.
Polyethers refers to polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.
The used catalyzer of the present invention can be one or more in the following alkyl rare earth compound:
Ln (C 6H 5) 3, a kind of in Ln=Sc, Y, the lanthanon;
LiLn(C 6H 5) 4，Ln＝La、Nd；
Ln(C 6H 4-R) 3，R＝CH 3、C 2H 5、OCH 3、OC 2H 5
A kind of in Ln=Sc, Y, the lanthanon;
Ln (C ≡ C-C 6H 5) 3, a kind of in Ln=Sc, Y, the lanthanon;
Ln (C 8H 6) (C 6H 5), a kind of in Ln=Sc, Y, the lanthanon;
LiLn (C 3H 5) 4THF, a kind of in Ln=Sc, Y, the lanthanon;
LiLn (C 3H 5) 4Dioxane, a kind of in the Ln=lanthanon;
Li 2Ln (C 3H 5) 5NTHF, a kind of in the Ln=lanthanon;
N=2.5 or 3
(η 3-C 3H 5) 2LnCl 5Mg 2(TMED) 2
A kind of in the Ln=lanthanon;
(η 3-C 4H 7) 2LnCl 5Mg 2(TMED) 2
A kind of in the Ln=lanthanon;
(η 3-C 4H 7) 2LnCl 5Mg 2(THF) 4
A kind of in the Ln=lanthanon.
Wherein: Dioxane is a dioxane.
Solvent is one or more in benzene, toluene, phenyl ether, two methyl-phenoxides, dioxane, tetrahydrofuran (THF), methylene dichloride, the trichloromethane.
The invention belongs to living polymerization, in reaction process, can add monomer and still can proceed polymerization.
The present invention can obtain high molecular weight polymers within a short period of time, productive rate reaches 50～95%, be up to 98%, can make molecular weight at 10,000～1,000,000 the high molecular even the polymkeric substance of ultra-high molecular weight, can prepare homopolymer, also can prepare the random copolymerization or the segmented copolymer of two kinds or three kinds lactones, the multipolymer that can also prepare lactone and polyethers, products obtained therefrom has excellent biodegradability and biocompatibility, is fabulous biomedical material, also can be applicable in the daily life field.
Embodiments of the invention are as follows: (wherein having used following writing a Chinese character in simplified form or code name)
M ν=M η: viscosity-average molecular weight
ε-Cl: 6-caprolactone
D, L-LA:D, L-rac-Lactide
PEG: polyoxyethylene glycol
Mn: number-average molecular weight
Mw: weight-average molecular weight
PD: molecular weight distribution
THF: tetrahydrofuran (THF)
M: concentration unit, mol/ liter
H: time unit, hour
The sign of polymericular weight is measured with GPC (gel permeation chromatograph) or viscosimetry.Be standard specimen with the polystyrene during GPC measures, poly-ε-Cl molecular weight [η]=9.94 * 10 by formula during viscosimetry is measured -5M η 0.82(30 ℃ of benzene solvents), J.V.Koleskeand R.D.Lundberg, J.Polym.Sci., Polym.phys.Ed., 7,897 (1969).
Poly-D, L-lactic acid molecules amount is by [η]=1.07 * 10 -4M η 0.75(37 ℃, the THF solvent) (Wise, Donald L.et, al; Drug Carriors Biol.Mecl., 1979,237)
Embodiment one:
In a drying is filled the reaction flask of nitrogen, band stirring, add the Y (C of 1.5ml ε-Cl and 0.24ml0.11M 6H 5) 3THF solution, in 70 ℃ the reaction 20 minutes after, termination reaction.Add the 20ml acetone solution, add a small amount of 5% hydrochloric acid again, precipitation, filtration in methyl alcohol, productive rate 86% after the product vacuum-drying, M ν=7.6 ten thousand, monomer/catalyst (mol ratio)=500.
Embodiment two:
In the prescription of embodiment one, add 7.5ml benzene, 70 ℃ are reacted half an hour, use the 5%HCl termination reaction, add 20ml benzene solubilizing reaction thing, and other are operated with embodiment one, get 1.32 gram polymkeric substance, productive rate 88%, M ν=6.8 ten thousand, monomer/catalyst (mol ratio)=500.
Embodiment three:
In the device with embodiment one, add the 0.4g polyethylene glycol 6000,3.6 gram D, L-LA, the THF solution that adds 0.14ml0.99M triphenyl neodymium, in 150 ℃ of reaction 2h, get multipolymer 3 grams, productive rate 75%, GPC measures Mn=1.6 ten thousand, Mw=3.5 ten thousand, PD=2.0, monomer/catalyst (mol ratio)=200.
Embodiment four:
With adding 4 gram D in the device of embodiment one, L-LA, the Sm (C of adding 0.15ml 0.12M 6H 4-CH 3) 3Benzole soln, at 170 ℃ of reaction 3h, the processing of product is with embodiment one, the poly-D of 3.7 grams, L-lactic acid, yield 92.5%, monomer/catalyst (mol ratio)=1500, M ν=11.9 ten thousand.
Embodiment five:
Add 2ml ε-Cl, 0.2ml 0.14M LiNd (C in the device of embodiment one 6H 5) 4Benzole soln, 160 ℃ the reaction 15 minutes, other is operated with embodiment one, productive rate 85%, M ν=17 ten thousand, monomer/catalyst (mol ratio)=600.
Embodiment six:
Add ε-Cl 1.8ml in the device with embodiment one, PEG6000 0.2 gram adds 0.2ml 0.14M LiNd (C 6H 5) 4Benzole soln, 80 ℃ of reaction half an hour, product use petroleum ether precipitation after with acetone solution, product after filtration after the drying 1.9 restrain multipolymers, productive rate 95%, monomer/catalyst (mol ratio)=600.
Embodiment seven:
In with the device of embodiment one, add 1ml ε-Cl, 10ml toluene, 0.12ml 0.15MSm (C 6H 5) 3THF solution, in 50 ℃ of reaction 1h, all the other are handled with embodiment one, must gather ε-Cl 0.98 and restrain productive rate 98%, M ν=11 ten thousand, monomer/catalyst (mol ratio)=500.
Embodiment eight:
In device, add D, L-LA2 gram, the LiLa (C of 10ml toluene 0.6ml 0.048M with embodiment one 6H 5) 4THF solution, in 70 ℃ of reaction 3h, other operate with embodiment one, must gather D, L-lactic acid 1.68 restrains, productive rate 84%, M ν=1.6 ten thousand.
Embodiment nine:
In device, add D with embodiment one, L-3-methyl-glycollide 4 grams, other operation and prescription are identical with embodiment four, must gather D, L-lactic acid and polyglycolic acid alternating copolymer 3.2 grams, productive rate 80%, monomer/catalyst (mol ratio)=1450.
Embodiment ten:
In with the device of embodiment one, add 1ml ε-Cl, 10ml toluene, 0.2ml 4.8 * 10 -2M LiLa (C 6H 5) 4THF solution, after 80 ℃ of reactions were added 1ml ε-Cl after 30 minutes, reacted 30 minutes again, all the other were operated with embodiment one, must gather ε-Cl productive rate is 70%, M ν=8.5 ten thousand, monomer/catalyst (mol ratio)=1800.
Embodiment 11:
In with the device of embodiment one, add 2 gram D, L-LA, 10ml THF, 0.2 gram PEG6000,0.5ml 0.2M (η 3-C 3H 5) 2SmCl 5Mg 2(TMED) 2THF solution, in 60 ℃ of polymerization 6h, other is operated with embodiment one, polymkeric substance 1.7 gram, productive rate 85%, monomer/catalyst (mol ratio)=100.
Embodiment 12:
With adding glycollide 2 grams, 0.2ml 0.14M Sm (C in the device of embodiment one 6H 4-CH 3) 3Benzole soln in 100 ℃ of reactions 20 minutes, gets polymkeric substance 1.9 grams, productive rate 95%, monomer/catalyst (mol ratio)=600.
Embodiment 13:
In device, add 2ml ε-Cl, 0.5ml 0.14M Y (C ≡ C-C with embodiment one 6H 5) 3THF solution, in 20 ℃ of polymerization 6h, product is handled with embodiment one, 1.6 the gram polymkeric substance, productive rate 80%, monomer/catalyst (mol ratio)=250.
Embodiment 14:
In device with embodiment one, add 5ml ε-Cl, add the Sm (C of 0.3ml 0.14M 6H 5) 3Benzole soln, in 50 ℃ of reaction 2h, all the other are handled with embodiment one, get 4.6 gram polymkeric substance, monomer/catalyst (mol ratio)=1000, Mw=27 ten thousand.
Embodiment 15:
In device, add 2 gram D, L-rac-Lactide, 2 gram glycollide, the Nd (2-CH of 0.2ml 0.112M with embodiment one 3OC 6H 4) 3Benzole soln, in 200 ℃ of reactions 30 minutes, all the other were with embodiment one, multipolymer 3 grams, productive rate 75%, monomer/catalyst (mol ratio)=700.
Embodiment 16:
In device, put into rac-Lactide 5 grams, phenyl ether the 2.0ml, (η of adding 0.14ml 0.5M with embodiment one 3-C 4H 7) 2SmCl 5Mg 2(TMED) 2THF solution, in 120 ℃ of reaction 24h, product 3.6 gram, productive rate 72%, monomer/catalyst (mol ratio)=500.
Embodiment 17:
In monomer and solvent formula, add the Nd (C of 0.45ml 0.1M with embodiment 16 6H 5) 3Benzole soln, in 140 ℃ of reaction 8h, polymkeric substance 4 gram, productive rate 80%, Mw=12.3 ten thousand.
Embodiment 18:
In device, add 2ml ε-Cl, 0.8 gram D, L-rac-Lactide, 0.2 gram polypropylene glycol, the LiLa (C of adding 0.2ml 0.8M with embodiment one 6H 5) 4THF solution, in 170 ℃ of reaction 8h, polymkeric substance 2 gram, productive rate 66.7%, monomer/catalyst (mol ratio)=100.
Embodiment 19:
In device, put into 2 gram D, L-rac-Lactide, 2ml dioxane, the LiGd (C of 0.25ml 0.1M with embodiment one 3H 5) 4The THF solution of Dioxane at 20 ℃ of polymerization 16h, gets polymkeric substance 1.4 grams, productive rate 70%, monomer/catalyst (mol ratio)=550.
Embodiment 20:
In device, add 1ml ε-Cl, CH with embodiment one 2Cl 23ml, the Li of adding 0.15ml 0.2M 2Pr (C 3H 5) 5The THF solution of 3THF in 10 ℃ of polymerization 10h, gets polymkeric substance 0.7 gram, productive rate 70%, monomer/catalyst (mol ratio)=300.
Embodiment 21:
In device, add 5 gram ε-Cl, 40ml benzene, the Nd (C of 0.25ml 0.14M with embodiment one 6H 5) 3, 0.25ml 0.2M Sm (C 6H 5) 3,, get polymkeric substance 4.2 grams, productive rate 84%, monomer/catalyst (mol ratio)=500 in 70 ℃ of polymerization 1h.
Embodiment 22:
In device with embodiment one, add 1.8 gram D, the L-rac-Lactide, 10mlTHF, catalyzer and amount are with embodiment 11, behind 50 ℃ of reaction 3h, add 0.2 gram PEG4000, after continuing reaction 3h, all the other are operated with embodiment one, get polymkeric substance 1.2 grams, productive rate 60%, monomer/catalyst (mol ratio)=100.
Embodiment 23:
Add 7ml benzene in the prescription of embodiment one, 5ml toluene, all the other operations get polymkeric substance 1 gram, productive rate 67% with embodiment one.
Embodiment 24:
Put into 1ml ε-Cl in the device of embodiment one, add the Y (C of 0.25ml 0.5M 8H 6) (C 6H 5) THF solution, 80 ℃ of reaction l0 seconds, all the other operates with embodiment one, polymkeric substance 1.2 restrain productive rate 60%, monomer/catalyst (mol ratio)=70.

Claims (6)

1. the synthetic method of a biodegradability polyester material is with δ-caprolactone, D, and the L-rac-Lactide, glycollide, D, one or more in L-3-methyl-glycollide are monomer, it is characterized in that catalyzer is LnR 3Type or LiLnR 4Type alkyl rare earth compound or (C 3H 5) 2LnCl 5Mg 2(TMED) 2, (C 4H 7) 2LnCl 5Mg 2(TMED) 2, (C 4H 7) 2LnCl 5Mg 2(THF) 4Type allyl group rare earth compounding; wherein Ln is a kind of in Sc, Y or the lanthanon; R is one or both in phenyl, substituted-phenyl, allyl group, substituted allyl, cyclooctatetraene base, the phenylacetylene base; monomer/catalyst (mol ratio) is 50～5000; under the protection of inert gas, polymerization time 10 seconds～24 hours, polymerization temperature is 0～200 ℃; also can add solvent and carry out solution polymerization, the weight ratio of monomer in solvent is 5%～50%.
2. the synthetic method of biodegradability polyester material according to claim 1 is characterized in that, also available polyethers is a comonomer, with 6-caprolactone, and D, the L-rac-Lactide, glycollide, D, one or more in L-3-methyl-glycollide carry out copolymerization.
3. the synthetic method of biodegradability polyester material according to claim 2 is characterized in that polyethers is one or more in polyoxyethylene glycol, polypropylene glycol, the polytetramethylene glycol.
4. the synthetic method of biodegradability polyester material according to claim 1 and 2 when it is characterized in that copolyreaction, can add all comonomers simultaneously, and also sectional adds.
5. the synthetic method of biodegradability polyester material according to claim 1 and 2 is characterized in that, catalyzer is Ln (C 6H 5) 3(in Ln=Sc, Y, the lanthanon a kind of), LiLn (C 6H 5) 4(Ln=La, Nd), Ln (C 6H 4-R) 3(R=CH 3, C 2H 5, OCH 3, OC 2H 5A kind of in Ln=Sc, Y, the lanthanon), LiLn (C 3H 5) 4THF (in Ln=Sc, Y, the lanthanon a kind of), Ln (C ≡ C-C 6H 5) 3(in Ln=Sc, Y, the lanthanon a kind of), Ln (C 8H 6) (C 6H 5) (in Ln=Sc, Y, the lanthanon a kind of), LiLn (C 3H 5) 4Dioxane (in the Ln=lanthanon a kind of), Li 2Ln (C 3H 5) 5NTHF (in the Ln=lanthanon a kind of, n=2.5 or 3), (η 3-C 3H 5) 2LnCl 5Mg 2(TMED) 2(in the Ln=lanthanon a kind of), (η 3-C 4H 7) 2LnCl 5Mg 2(TMED) 2(in the Ln=lanthanon a kind of), (η 3-C 4H 7) 2LnCl 5Mg 2(THF) 4In (in the Ln=lanthanon a kind of) one or more.
6. the synthetic method of biodegradability polyester material according to claim 1 and 2, it is characterized in that the solvent of solution polymerization is one or more in benzene, toluene, tetrahydrofuran (THF), methylene dichloride, trichloromethane, dioxane, phenyl ether, two methyl-phenoxides.
CN 96117591 1996-06-24 1996-06-24 Synthetic method for biodegradability polyester material Pending CN1146466A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000204109A (en) * 1997-11-27 2000-07-25 Enichem Spa Lanthanide-based catalytic complex for, conjugated diene (co) polymerization
CN1331913C (en) * 2002-02-05 2007-08-15 重庆永通信息工程实业有限公司 Synthesis and application of post-operative adhesion-preventing material
CN100453581C (en) * 2003-10-24 2009-01-21 住友电工超效能高分子股份有限公司 Biodegradable material and process for producing the same
US7635341B2 (en) 2003-05-19 2009-12-22 Doorzand Trocar Protector B.V. Insertion sleeve assembly
CN101343354B (en) * 2008-08-29 2011-05-04 胡权 Poly-lactide, poly-glycolide and preparation for copolymer of the same
CN101302280B (en) * 2007-05-10 2011-09-14 东丽纤维研究所（中国）有限公司 Rare earth compound-containing L-lactic acid and D-lactic acid block copolymer, and preparation thereof
CN101817923B (en) * 2009-02-26 2012-10-10 惠州华阳医疗器械有限公司 Catalyst/initiator system
CN110003455A (en) * 2018-01-05 2019-07-12 中国石油化工股份有限公司 A kind of preparation method of carbon monoxide-olefin polymeric and polylactide

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000204109A (en) * 1997-11-27 2000-07-25 Enichem Spa Lanthanide-based catalytic complex for, conjugated diene (co) polymerization
CN1331913C (en) * 2002-02-05 2007-08-15 重庆永通信息工程实业有限公司 Synthesis and application of post-operative adhesion-preventing material
US7635341B2 (en) 2003-05-19 2009-12-22 Doorzand Trocar Protector B.V. Insertion sleeve assembly
CN100453581C (en) * 2003-10-24 2009-01-21 住友电工超效能高分子股份有限公司 Biodegradable material and process for producing the same
CN101302280B (en) * 2007-05-10 2011-09-14 东丽纤维研究所（中国）有限公司 Rare earth compound-containing L-lactic acid and D-lactic acid block copolymer, and preparation thereof
CN101343354B (en) * 2008-08-29 2011-05-04 胡权 Poly-lactide, poly-glycolide and preparation for copolymer of the same
CN101817923B (en) * 2009-02-26 2012-10-10 惠州华阳医疗器械有限公司 Catalyst/initiator system
CN110003455A (en) * 2018-01-05 2019-07-12 中国石油化工股份有限公司 A kind of preparation method of carbon monoxide-olefin polymeric and polylactide
CN110003455B (en) * 2018-01-05 2021-09-21 中国石油化工股份有限公司 Catalyst composition and preparation method of polylactide

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