CN103570884A - Preparation method for maleic anhydride-modified polylactic-co-glycolic acid - Google Patents
Preparation method for maleic anhydride-modified polylactic-co-glycolic acid Download PDFInfo
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- CN103570884A CN103570884A CN201310564511.1A CN201310564511A CN103570884A CN 103570884 A CN103570884 A CN 103570884A CN 201310564511 A CN201310564511 A CN 201310564511A CN 103570884 A CN103570884 A CN 103570884A
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Abstract
The invention relates to a preparation method for maleic anhydride-modified polylactic-co-glycolic acid. The preparation method comprises the following steps: (1) adding 70-90 parts by weight of D,L-lactide, 20-30 parts by weight of glycolide, and 5-10 parts by weight of maleic anhydride into an ampoule bottle, and then adding 0.01-0.03 parts by weight of stannous octoate [Sn(Oct)2]; adding BPO (Benzoyl peroxide), the addition amount of which accounts for 1-5% of the weight of maleic anhydride; performing vacuum drying, highly vacuumizing to 10Pa below through a diffusion pump, and sealing a pipe through an alcohol blast burner; (2) performing polymerization reaction at 130-170 DEG C, for reaction time of 12-60 hours; (3) taking out a crude product, dissolving the crude product into trichloromethane to prepare a 5-10wt% solution, the precipitating in 3-5 times of ethanol, repeatedly purifying, performing vacuum drying to the product to constant weight, to obtain the maleic anhydride-modified polylactic-co-glycolic acid (MPLGA). The maleic anhydride-modified polylactic-co-glycolic acid has the following advantages of being better in hydrophilic performance and biocompatibility, more excellent in mechanical performance, and providing good basis and possibility for the follow-up improvement of the material due to the introduction of acid anhydride bonds.
Description
Technical field
The present invention relates to the production technical field of Biodegradable polymer material, be specifically related to a kind of preparation method with good biocompatibility and biodegradability, poly-the third glycollide (MPLGA) of the good modification of hydrophilicity.
Background technology
The cartilage defect that physical abuse or sacroiliitis cause is the difficult problem that faced clinically for a long time always, along with developing rapidly of organizational project in recent years, for the damaged reparation of cartilaginous tissue and regeneration provide good theoretical foundation and practical basis.Desirable cartilage tissue engineered rack material should possess 3 D stereo vesicular structure, good biocompatibility and biological degradability, certain plasticity-and physical strength, the Modulatory character of surface microenvironment, good osteoconductive and osteoinductive, be beneficial to cell adhesion, proliferation and differentiation and blood vessel, neural growing into.
Poly-the third glycollide (PLGA) is one of most widely used cytoskeleton starting material in current Tissue Engineering Study, there is nontoxic, good biocompatibility, the excellent properties such as can be in vivo degradable, have the advantage of poly(lactic acid) (PLA) and two kinds of polyester of polyglycolic acid (PGA) concurrently, its degree of crystallinity is very low, it is unformed shape toughness material, be easy to spinning, fibre strength is higher, extensibility is moderate, can, by regulating the ratio of two kinds of monomers to carry out the degradation speed of controlled material, it be had a wide range of applications at aspects such as slow-release material, operating sutures, organizational projects.But its application that PLGA has still existed some drawbacks limit, as its hydrophilicity and cell adhesion forces a little less than, biomechanical property is not strong, and owing to lacking abundant active group, be unfavorable for that covalency is introduced the biogenic signaling molecules such as polypeptide, collagen wherein, make it can not become the real biological active materials with biospecificity.Therefore must carry out further modification to it, to improve its over-all properties.
Maleic anhydride (MAH) is a kind of polyfunctional group material of eubolism in vivo, and the structure of the intermediate fumaric acid of its hydrolysate toxilic acid during with organism tricarboxylic acid cycle is identical, thus its at human body, to use be safe.Utilize the free radical reaction of the carbon-to-carbon double bond in maleic anhydride can be grafted in PLGA skeleton, its anhydride bond hydrolyzable generates two hydrophilic carboxyls, thereby improves wetting ability and the cell biological consistency of PLGA.In addition, maleation forms in addition comb-branched structure and cross-linked network structure in polymer materials design, at aspects such as material interface increase-volume, formation fluorescent mark polymkeric substance, has a wide range of applications.
In recent years, more and more higher along with to tissue engineering bracket material performance requriements, is imperative to the modification of timbering material.Maleic anhydride modified poly(lactic acid) has had a large amount of research at home and abroad, but with maleic anhydride, the modification of PLGA is also rarely had to report based on this, therefore has good researching value and application prospect.
Summary of the invention
The object of this invention is to provide a kind of preparation method with poly-the third glycollide of modification that good biocompatibility, hydrophilicity are good.
A preparation method for maleic anhydride modified poly-the third co-glycolide polymers, concrete steps are as follows:
(1) according to parts by weight of raw materials, will comprise 70 ~ 80 parts of D, L-rac-Lactide, 20 ~ 30 parts of glycollide and 5 ~ 10 parts of maleic anhydrides add in ampoule, then add 0.01 ~ 0.03 part of stannous octoate (Sn (Oct)
2); Add benzoyl peroxide (BPO), its add-on is 1 ~ 5 % of maleic anhydride weight; Pumping high vacuum tube sealing after vacuum-drying 12 ~ 24 h; High vacuum is obtained by diffusion pump, vacuumizes 0.5 ~ 1 h under normal temperature, makes pressure in ampoule lower than 10 Pa, then use alcohol blast burner tube sealing;
(2) ampoule after tube sealing is put into thermostat container, after raw material is melted at 100 ℃, shake up, then at 130 ~ 170 ℃ of temperature, react, take out after reacting 12 ~ 60 h;
(3) finally break ampoule into pieces, crude product is dissolved in trichloromethane, be mixed with 5 ~ 10wt% solution, then splash in the ethanol of 3～5 times and be precipitated out, repeat to purify, until washing lotion is neutral, the product vacuum-drying after purification, to constant weight, obtains maleic anhydride modified poly-the third co-glycolide polymers (MPLGA);
In step (1), described D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying; Described glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
Described maleic anhydride modified poly-the third co-glycolide polymers, its structural formula is suc as formula shown in I:
In the present invention, the synthetic of MPLGA is at D, and on the basis of the ring opening copolymer of L-rac-Lactide and two kinds of monomers of glycollide, maleic anhydride is grafted to by radical polymerization in the skeleton of multipolymer, and two reactions are all carried out in ampoule.
Product of the present invention (maleic anhydride modified poly-the third co-glycolide polymers) is faint yellow solid, and hardness is large, and second-order transition temperature is 50 ~ 60 ℃, and titration measuring maleic anhydride grafting ratio is 2 ~ 3%, and molecular weight can reach more than 50,000.The contact angle that obtains MPLGA by mensuration is 89.08 °.
Because the high low energy of second-order transition temperature reflects the kind of superpolymer to a certain extent, the PLGA second-order transition temperature of preparation is 62.5 ℃ of left and right after measured, the second-order transition temperature of MPLGA is 52.5 ℃ of left and right, PLGA and the MPLGA difference in second-order transition temperature, can illustrate that maleic anhydride has successfully been linked in PLGA skeleton, changed its chemical structure, thereby made it in second-order transition temperature, have certain difference.According to the difference of contact angle, the difference of hydrophilicity and hydrophobicity that can judgement place bi-material, the contact angle that obtains MPLGA by mensuration be 89.08 ° higher than 80.56 ° of PLGA, illustrate that maleic anhydride has successfully been linked in the skeleton of PLGA, because there is the existence of anhydride bond in MPLA, anhydride bond is hydrophobic group, if anhydride bond is hydrolyzed to hydrophilic-COOH, has obvious hydrophilic interaction, but the method that adopts Static Water contact angle is measured the hydrophilic and hydrophobic of MPLA, minute is short, anhydride bond fails to be hydrolyzed, therefore show obvious hydrophobic performance.
Poly-the third glycollide of the resulting modification of the present invention is compared and is had the following advantages with poly-the third glycollide:
(1) hydrophilicity and biocompatibility are better, the access of maleic anhydride makes to have in the skeleton of PLGA the existence of anhydride bond, in its degradation process, anhydride bond can be hydrolyzed and generate two hydrophilic carboxyls, thereby improves greatly hydrophilicity and cell adhesion and the proliferative of material.
(2) mechanical property is more excellent, and the modifying process of maleic anhydride exists two keys and PLGA molecule to carry out suitable being cross-linked, thereby the performance of poly-the third glycollide is had greatly changed, its crosslinked mechanical property that can further improve material.
(3) introducing of anhydride bond can also provide for the follow-up improvement of material good basis and possibility; as acid anhydrides bond energy and aliphatie diamine generation N-acylation reaction; thereby introducing amine substance, can further improve the hydrophilicity of material and cellular affinity etc.
Embodiment
Below by specific embodiment, the present invention is described in further detail, and described raw material umber, except special instruction, is parts by weight.
Embodiment 1:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 70 g, glycollide 30 g and maleic anhydride 5g pack in ampoule, then add that 0.2g benzoyl peroxide (BPO) is made initiator, 0.01g stannous octoate is made catalyzer, vacuum-drying 12h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by 130 ℃ of reaction 36 h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 5wt% solution, then splash in the ethanol of 3 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=11651, M
w/ M
n=1.276.
Embodiment 2:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 70 g, glycollide 20 g and maleic anhydride 8g pack in ampoule, then add that 0.08 g benzoyl peroxide (BPO) is made initiator, 0.02g stannous octoate is made catalyzer, vacuum-drying 12 h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by 140 ℃ of reaction 24 h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 10wt% solution, then splash in the ethanol of 5 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24 h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=23722, M
w/ M
n=1.294.
Embodiment 3:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 75 g, glycollide 25 g and maleic anhydride 6 g pack in ampoule, then add that 0.3 g benzoyl peroxide (BPO) is made initiator, 0.03 g stannous octoate is made catalyzer, vacuum-drying 12 h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by 150 ℃ of reaction 36 h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 6wt% solution, then splash in the ethanol of 4 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24 h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=42125, M
w/ M
n=1.322.
Embodiment 4:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 80g, glycollide 30 g and maleic anhydride 10 g pack in ampoule, then add that 0.3 g benzoyl peroxide (BPO) is made initiator, 0.03 g stannous octoate is made catalyzer, vacuum-drying 12 h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by 160 ℃ of reaction 48 h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 7wt% solution, then splash in the ethanol of 5 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24 h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=33979, M
w/ M
n=1.374.
Embodiment 5:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 80 g, glycollide 30 g and maleic anhydride 9 g pack in ampoule, then add that 0.3 g benzoyl peroxide (BPO) is made initiator, 0.02 g stannous octoate is made catalyzer, vacuum-drying 12 h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by 170 ℃ of reaction 12 h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 8wt% solution, then splash in the ethanol of 3 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24 h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=53144, M
w/ M
n=1.269.
Embodiment 6:
Self-control D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying;
Self-control glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
By D, L-rac-Lactide 75 g, glycollide 25 g and maleic anhydride 8 g pack in ampoule, then add that 0.3 g benzoyl peroxide (BPO) is made initiator, 0.03 g stannous octoate is made catalyzer, vacuum-drying 12 h.After dry, take out, diffusion pump vacuumizes 1 h, and low vacuum is tube sealing after 10 Pa, by the 140 ℃ of reaction 60h in thermostatic drying chamber of the ampoule after tube sealing.Crude product is purified: crude product is dissolved in trichloromethane, is mixed with 9wt% solution, then splash in the ethanol of 4 times and be precipitated out, repeat to purify three times, to washing lotion, be neutral, 40 ℃ of vacuum-drying 24 h of final product, obtain faint yellow solid MPLGA.Products obtained therefrom M
n=23663, M
w/ M
n=1.101.
Claims (1)
1. a preparation method for maleic anhydride modified poly-the third co-glycolide polymers, concrete steps are as follows:
(1) according to parts by weight of raw materials, will comprise 70 ~ 80 parts of D, L-rac-Lactide, 20 ~ 30 parts of glycollide and 5 ~ 10 parts of maleic anhydrides add in ampoule, then add 0.01 ~ 0.03 part of stannous octoate (Sn (Oct)
2); Add benzoyl peroxide (BPO), its add-on is 1 ~ 5 % of maleic anhydride weight; Pumping high vacuum tube sealing after vacuum-drying 12 ~ 24 h; High vacuum is obtained by diffusion pump, vacuumizes 0.5 ~ 1 h under normal temperature, makes pressure in ampoule lower than 10 Pa, then use alcohol blast burner tube sealing;
(2) ampoule after tube sealing is put into thermostat container, after raw material is melted at 100 ℃, shake up, then at 130 ~ 170 ℃ of temperature, react, take out after reacting 12 ~ 60 h;
(3) finally break ampoule into pieces, crude product is dissolved in trichloromethane, be mixed with 5 ~ 10wt% solution, then splash in the ethanol of 3～5 times and be precipitated out, repeat to purify, until washing lotion is neutral, the product vacuum-drying after purification, to constant weight, obtains maleic anhydride modified poly-the third co-glycolide polymers (MPLGA);
In step (1), described D, L-rac-Lactide: adopt decompression method, with D, Pfansteihl is raw material, and after 140～160 ℃ of cyclodehydrations, 250 ℃ of open loop cracking obtain thick D, L-rac-Lactide, obtains the D of needle-like, L-rac-Lactide crystal through purifying; Described glycollide: adopt decompression method, take oxyacetic acid as raw material, after 150～170 ℃ of cyclodehydrations, 260 ℃ of open loop cracking obtain thick glycollide, obtains the glycollide crystal of sheet through purifying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103864999A (en) * | 2014-03-27 | 2014-06-18 | 南通纺织职业技术学院 | Preparation method for maleic anhydride-modified poly(lactic-co-glycolic acid) copolymer |
| CN103865046A (en) * | 2014-03-27 | 2014-06-18 | 南通纺织职业技术学院 | Synthetic process for maleic anhydride-modified poly(lactic-co-glycolic acid) |
| CN104177553A (en) * | 2014-08-25 | 2014-12-03 | 湖南科技大学 | Preparation method of ethylenediamine modified maleic anhydride polylactide-glycolide polymer |
| CN105315412A (en) * | 2015-11-23 | 2016-02-10 | 湖南科技大学 | Technology for preparing high-molecular-weight MPLGA by directly grafting maleic anhydride onto PLGA |
| CN114957634A (en) * | 2022-07-04 | 2022-08-30 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
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| WO2013008156A1 (en) * | 2011-07-08 | 2013-01-17 | Universita' Degli Studi Di Milano | Branched lactic acid polymers with high viscosity in the molten state and high shear sensitivity, and nanocomposites thereof |
| CN102898660A (en) * | 2011-07-26 | 2013-01-30 | 东南大学 | Preparation method of hydrogel for three-dimensional culture of tumor cells |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050085605A1 (en) * | 2002-12-18 | 2005-04-21 | Aruna Nathan | Functionalized polymers for medical applications |
| WO2013008156A1 (en) * | 2011-07-08 | 2013-01-17 | Universita' Degli Studi Di Milano | Branched lactic acid polymers with high viscosity in the molten state and high shear sensitivity, and nanocomposites thereof |
| CN102898660A (en) * | 2011-07-26 | 2013-01-30 | 东南大学 | Preparation method of hydrogel for three-dimensional culture of tumor cells |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864999A (en) * | 2014-03-27 | 2014-06-18 | 南通纺织职业技术学院 | Preparation method for maleic anhydride-modified poly(lactic-co-glycolic acid) copolymer |
| CN103865046A (en) * | 2014-03-27 | 2014-06-18 | 南通纺织职业技术学院 | Synthetic process for maleic anhydride-modified poly(lactic-co-glycolic acid) |
| CN103865046B (en) * | 2014-03-27 | 2016-04-13 | 南通纺织职业技术学院 | A kind of synthesis technique of maleic anhydride modified poly lactic coglycolic acid |
| CN103864999B (en) * | 2014-03-27 | 2017-01-18 | 南通纺织职业技术学院 | Preparation method for maleic anhydride-modified poly(lactic-co-glycolic acid) copolymer |
| CN104177553A (en) * | 2014-08-25 | 2014-12-03 | 湖南科技大学 | Preparation method of ethylenediamine modified maleic anhydride polylactide-glycolide polymer |
| CN104177553B (en) * | 2014-08-25 | 2016-08-17 | 湖南科技大学 | The preparation method of poly-third co-glycolide polymers of ethylenediamine modified maleic anhydridization |
| CN105315412A (en) * | 2015-11-23 | 2016-02-10 | 湖南科技大学 | Technology for preparing high-molecular-weight MPLGA by directly grafting maleic anhydride onto PLGA |
| CN114957634A (en) * | 2022-07-04 | 2022-08-30 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
| CN114957634B (en) * | 2022-07-04 | 2023-12-22 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
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