CN111019109A - Poly D-lactic acid-isopropylidene glucose diblock copolymer material and preparation method thereof - Google Patents

Poly D-lactic acid-isopropylidene glucose diblock copolymer material and preparation method thereof Download PDF

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CN111019109A
CN111019109A CN201911353865.5A CN201911353865A CN111019109A CN 111019109 A CN111019109 A CN 111019109A CN 201911353865 A CN201911353865 A CN 201911353865A CN 111019109 A CN111019109 A CN 111019109A
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lactic acid
poly
glucose
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isopropylidene
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高勤卫
朱前进
祁俐燕
刘婷婷
常开新
曹丹
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Nanjing Forestry University
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Nanjing Forestry University
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract

The invention discloses a diblock copolymer material of poly D-lactic acid-isopropylidene glucose and a preparation method thereof, belonging to the technical field of high polymer materials.A diblock copolymer is prepared by taking poly D-lactic acid and hydroxyl protected diisopropylidene glucose as raw materials and carrying out melt polymerization reaction for 4-12 h under the conditions that the molar ratio of 1, 2, 5, 6-oxygen-diisopropylidene glucose to poly D-lactic acid is more than 4: 1, the pressure is 10-300 Pa and the temperature is 160-200 ℃, and the specific optical rotation [ α ] of the diblock copolymer material]25 DAbout +145, a melting temperature of about 148 ℃ and a crystallinity of about 49%, which are similar to those of poly-D-lactic acid, but the copolymer materialIs more hydrophilic than poly-D-lactic acid, and has a contact angle of about 72 °, while the contact angle of poly-D-lactic acid is 85 °.

Description

Poly D-lactic acid-isopropylidene glucose diblock copolymer material and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of high polymer materials, and particularly relates to a poly D-lactic acid-isopropylidene glucose diblock copolymer material and a preparation method thereof.
Background art:
polylactic acid (PLA) is a bio-based green thermoplastic derived from biomass that can ultimately be decomposed to convert to carbon dioxide, water, and humus. PLA includes two optical isomers of poly L-lactic acid (PLLA) and poly D-lactic acid (PDLA), the specific optical rotation of PLLA is-160, and the specific optical rotation of PDLA is +160, and the optical activity of the PLA has a significant effect on the PLA performance. PLA has good degradability and mechanical properties, and can be used in the fields of biomedicine, packaging, textile fibers and the like. However, polylactic acid has poor heat resistance and low hydrophilicity, and thus its application is limited. Thus, PLA needs to be modified to improve its properties. Copolymerization modification is one of the most important ways for improving the performance of polylactic acid, and is copolymerized with hydrophilic monomers or polymers such as monosaccharide, polyethylene glycol, polysaccharides and the like, and the crystallization performance, degradation speed, hydrophilicity and the like of the polylactic acid material are controlled by adjusting factors such as the molecular weight, the types of the comonomers, the molecular chain structure and the like of the copolymer.
The polylactic acid-CS-CEO composite fiber has good antibacterial performance and has wide application prospect in food packaging (Nanomaterials, 2017, 7 (7): 194 and 207.). Cheng et al firstly prepare Thermoplastic Starch (MTPs) functionalized by Maleic Anhydride (MA), take an epoxy chain extender (REC) as a compatibilizer, prepare a polylactic acid blending material PIA/MTPS/REC by a melt blending method, so that the mechanical properties of the blending material are obviously improved, the crystallization capacity of the blending material is reduced, the solvent resistance is improved (the blending of the polylactic acid blending material PIA/MTPS/REC is improved (the engineering sugar is used as a compatibilizer, the polylactic acid blending material PIA/MTPS/REC is prepared by a melt blending method, the polylactic acid blending material PIA/MTPS/REC is prepared by a simple melt blending method, the polylactic acid blending material PIA/MTPS/REC), the polylactic acid blending material PIA/MTPS/REC is prepared by a simple melt blending method, the polylactic acid blending method, polylactic acid.
When the polylactic acid is modified by copolymerization of monosaccharide and polysaccharide, the molecular chain structure of the copolymer is difficult to control because the saccharide molecules contain a large amount of hydroxyl groups, and the properties of the obtained copolymer are also difficult to control, resulting in unstable properties of the material. Among them, glucose contains 5 hydroxyl groups, and when it is copolymerized with PLA, all hydroxyl groups may participate in the reaction, so that the number of hydroxyl groups of glucose and the number of PLA segments in the copolymer are difficult to control, resulting in unstable performance.
Aiming at the problem that the molecular chain structure of the copolymer is difficult to control when the polylactic acid is modified by glucose, the invention adopts a hydroxyl protection method to regulate the hydroxyl number of the glucose, and prepares the poly D-lactic acid-isopropylidene glucose diblock copolymer by melt polymerization. The copolymerization of glucose and poly D-lactic acid can improve the hydrophilicity and comprehensive performance of the polylactic acid material and expand the application of the polylactic acid material in the fields of drug carriers, medical materials and the like.
The invention content is as follows:
aiming at the problem that the molecular chain structure of a copolymer is difficult to control when glucose is modified by polylactic acid, the invention firstly adopts an efficient, green and environment-friendly hydroxyl protection method to prepare 1, 2; 5, 6-oxo-diisopropylidene glucose (IPG). The IPG only contains one hydroxyl group and four ether bonds, and when the IPG is copolymerized with polylactic acid, the molecular chain structure of the copolymer can be regulated and controlled to form a poly D-lactic acid-isopropylidene glucose diblock copolymer, so that the hydrophilicity of the polylactic acid material is improved.
The technical scheme adopted for achieving the purpose of the invention is as follows:
the invention takes D-lactic acid and glucose as raw materials, stannous isooctanoate (Sn (Oct)2) Stannous chloride or p-toluenesulfonic acid is used as a catalyst, and a hydroxyl protection method and a direct melt polycondensation method are adopted to prepare the diblock copolymer.
The preparation process of the glucose and polylactic acid copolymer comprises the following steps: (1) preparing 1, 2 by a hydroxyl protection method; 5, 6-oxo-diisopropylidene glucose (IPG). 10g of glucose and 200ml of acetone are added into a reactor, stirred and added with proper amount of zinc chloride and phosphoric acid (the mol ratio is 1: 0.1) in sequence, and the mixture reacts for 30 hours at room temperature and normal pressure. Dropwise adding 50% NaOH aqueous solution under rapid stirring, adjusting the pH value of a reaction system to 8.0, carrying out suction filtration, washing for 2-3 times by using acetone until filtrate is colorless and transparent, carrying out rotary evaporation on the filtrate, dissolving the obtained solid by using trichloromethane, carrying out water washing extraction for 2-3 times, carrying out rotary evaporation on the obtained trichloromethane solution, recrystallizing the obtained sample by using ethyl acetate and petroleum ether for 2-3 times, and obtaining IPG (isopropyl-propyl-gallate) of a white needle crystal. (2) Preparation of poly D-lactic acid-isopropylidene glucose diblock copolymer (PDLAIPG). Weighing a certain amount of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting at constant temperature under normal pressure for 1h, then reducing the pressure to 200Pa for 4h, adding a catalyst (the dosage of the catalyst is 0.3-0.5 wt% of the total mass of the D-lactic acid), heating to 160-200 ℃, reducing the pressure to below 100Pa for reacting for 4-12 h to obtain poly D-lactic acid, adding IPG into a reaction system, wherein the molar ratio of the IPG to PDLA is more than 4: 1, and reacting for 4-12 h under the conditions of the pressure of 10-300 Pa and the temperature of 160-200 ℃. Dissolving the obtained product with chloroform, precipitating with excessive methanol, and vacuum drying the precipitate to obtain poly D-lactic acid-isopropylidene glucose diblock copolymer.
Further, the copolymer can also be prepared by the following steps: dissolving poly D-lactic acid obtained by melt polymerization with chloroform, precipitating with excessive methanol, and vacuum drying the separated precipitate at 50 deg.C for 10h to obtain purified poly D-lactic acid. And melting the purified poly D-lactic acid, adding IPG and a catalyst (the dosage of the catalyst is 0.3-0.5 wt% of the total mass of the D-lactic acid), wherein the molar ratio of the IPG to the PDLA is more than 4: 1, and reacting for 4-12 h under the conditions that the pressure is 10-300 Pa and the temperature is 160-200 ℃ to prepare the poly D-lactic acid-isopropylidene glucose diblock copolymer.
Furthermore, the catalyst is any one of stannous chloride, stannous isooctanoate and p-toluenesulfonic acid, and the dosage of the catalyst is 0.3-0.5 wt% of the total mass of the D-lactic acid.
Further, when the molar ratio of the IPG to the poly D-lactic acid is more than 4: 1, a diblock copolymer can be prepared.
Furthermore, the number of the poly D-lactic acid chain segments and the molecular mass can be regulated and controlled by controlling the melt polymerization time.
Further, the specific optical rotation of the PDLAIPG material [ α]25 DAbout +145, a melting temperature of about 148 ℃, and a crystallinity of about 49%, similar to PDLA, but more hydrophilic than poly D-lactic acid, the copolymer had a contact angle of about 72 °, and PDLA had a contact angle of 85 °.
The invention adopts hydroxyl protection method and direct melt polycondensation method to prepare poly D-lactic acid-isopropylidene glucose copolymer material, which can control the molecular chain structure of the copolymer and the length of poly D-lactic acid chain segment, and can be better used as slow-release drug carrier.
Description of the drawings:
FIG. 1 is a schematic structural diagram of a poly D-lactic acid-isopropylidene glucose diblock copolymer of the present invention.
FIG. 2 is a scheme for the synthesis of poly D-lactic acid-isopropylidene glucose diblock copolymer of the invention.
FIG. 3 is a drawing showing a poly-D-lactic acid-isopropylidene glucose diblock copolymer of the invention1H-nuclear magnetic resonance spectrum.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to the accompanying drawings and specific examples and comparative examples. The specific material ratios, process conditions and results described in the examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1:
the poly D-lactic acid-isopropylidene glucose diblock copolymer was prepared using the synthetic route shown in FIG. 2. (1) Preparing 1, 2 by a hydroxyl protection method; 5, 6-oxo-diisopropylidene glucose (IPG). 10g of glucose and 200ml of acetone are added into a reactor, stirred and added with proper amount of zinc chloride and phosphoric acid (the mol ratio is 1: 0.1) in sequence, and the mixture reacts for 30 hours at room temperature and normal pressure. Dropwise adding 50% NaOH aqueous solution under rapid stirring, adjusting the pH value of a reaction system to 8.0, carrying out suction filtration, washing for 2-3 times by using acetone until filtrate is colorless and transparent, carrying out rotary evaporation on the filtrate, dissolving the obtained solid by using trichloromethane, carrying out water washing extraction for 2-3 times, carrying out rotary evaporation on the obtained trichloromethane solution, and recrystallizing the obtained sample by using ethyl acetate and petroleum ether for 2-3 times to obtain the IPG of a white needle crystal. (2) And (3) preparing a poly D-lactic acid-isopropylidene glucose copolymer. Weighing 100g of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting for 1h under constant temperature at normal pressure, then reducing the pressure to 200Pa, reacting for 4h, adding a catalyst stannous isooctanoate (the mass is 0.5 wt% of PDLA), heating to 180 ℃, reducing the pressure to below 10Pa, reacting for 4h to obtain poly D-lactic acid, adding IPG into a reaction system, wherein the molar ratio of IPG to PDLA is 4: 1, and reacting for 8h at 100Pa and 170 ℃. Dissolving the obtained product with chloroform, separating out excessive methanol, and vacuum drying the precipitate to obtain the poly D-lactic acid-isopropylidene glucose diblock copolymer. By using1Molecular chain of the copolymer obtained by H-NMR analysis (shown in FIG. 3) has a diblock structure of PDLA and IPG (shown in FIG. 1). The diblock copolymer has a weight average relative molecular mass of 19500 and a specific optical rotation [ α ]]25 DHas a melting point of 147 deg.C, a crystallinity of 42% and a water contact angle of 74 deg.C.
Example 2:
IPG was prepared using the method in example 1. Weighing 100g of D-lactic acid, adding into a reactor, heating to 150 ℃, reacting at constant temperature under normal pressure for 1h, then reducing the pressure to 200Pa for 4h, adding catalyst stannous isooctanoate (the mass is 0.5 wt% of PDLA), heating to 180 ℃, reducing the pressure to below 10Pa for reacting for 10h to obtain poly D-lactic acid, and adding into a reaction systemAdding IPG, the mol ratio of IPG to PDLA is 8: 1, and reacting for 6h under the conditions of 10Pa and 200 ℃. Dissolving the obtained product with chloroform, separating out excessive methanol, and vacuum drying the precipitate to obtain the poly D-lactic acid-isopropylidene glucose diblock copolymer. By using1Molecular chain of the copolymer obtained by H-nuclear magnetic resonance spectrum (shown in FIG. 3) analysis has a PDLA and IPG diblock structure (shown in FIG. 1). The diblock copolymer has a weight average relative molecular mass of 36000 and a specific optical rotation [ α ]]25 DAbout +140, melting point 148 ℃, crystallinity of 49% and water contact angle of 72 °.
Example 3:
IPG was prepared using the method in example 1. Weighing 100g of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting at constant temperature under normal pressure for 1h, then reducing the pressure to 200Pa for 4h, adding a catalyst of stannous chloride (the mass is 0.3 wt% of PDLA), heating to 180 ℃, reducing the pressure to below 10Pa for 6h, reacting to obtain poly D-lactic acid, adding IPG into a reaction system, wherein the molar ratio of IPG to PDLA is 10: 1, and reacting at 10Pa and 200 ℃ for 8 h. Dissolving the obtained product with chloroform, separating out excessive methanol, and vacuum drying the precipitate to obtain the poly D-lactic acid-isopropylidene glucose diblock copolymer. By using1The molecular chain of the diblock copolymer obtained by H-NMR analysis had a structure in which PDLA and IPG diblock form (the molecular chain structure is shown in FIG. 1). The weight average relative molecular mass of the diblock copolymer was 28000, and the specific optical rotation [ α ]]25 DAbout +142, melting point 146 ℃, crystallinity of 48%, water contact angle of 75 °.
Example 4:
IPG was prepared using the method in example 1. The poly D-lactic acid is prepared by taking D-lactic acid as a raw material and adopting a melt polymerization method. The PDLA obtained was purified by the solution-precipitation method of example 1. Melting purified poly D-lactic acid in a four-neck flask, adding IPG and 0.5 wt% of stannous chloride, wherein the molar ratio of IPG to PDLA is 5: 1, then reducing the pressure to 300Pa, and reacting for 6 h. The obtained product is dissolved by trichloromethane, and excessive methanol solution is separated out to obtain precipitate. The precipitate was separated by suction filtration. Vacuum drying the precipitate at 50 deg.C for 10 hr to obtain polymerD-lactic acid-isopropylidene glucose diblock copolymer. By using1The molecular chain of the diblock copolymer obtained by H-NMR spectrum analysis had a structure of PDLA and IPG diblock (the molecular chain structure is shown in FIG. 1). The diblock copolymer had a weight average relative molecular mass of 16400 and a specific optical rotation [ α ]]25 DAbout +141, melting point 145 ℃, crystallinity 44%, water contact angle 78 °.
Comparative example 1:
weighing 100g of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting at constant temperature under normal pressure for 1h, then reducing the pressure to 200Pa for 4h, adding a catalyst of stannous chloride (the mass is 0.3 wt% of PDLA), heating to 180 ℃, reducing the pressure to below 10Pa for reacting for 8h to obtain poly D-lactic acid, dissolving the obtained poly D-lactic acid with trichloromethane, precipitating and separating out with excessive methanol, and drying the separated precipitate at 50 ℃ for 10h in vacuum to obtain purified poly D-lactic acid, wherein the weight average relative molecular mass of the PDLA is 12000, and the specific optical rotation is [ α ]]25 DHas a melting point of 148 ℃, a crystallinity of 49 percent and a water contact angle of 85 degrees.
Comparative example 2:
IPG was prepared using the method in example 1. Weighing 100g of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting at constant temperature under normal pressure for 1h, then reducing the pressure to 200Pa for 4h, adding a catalyst of stannous chloride (the mass is 0.5 wt% of PDLA), heating to 180 ℃, reducing the pressure to below 10Pa for 6h, reacting to obtain poly D-lactic acid, adding IPG into a reaction system, wherein the molar ratio of IPG to PDLA is 1: 1, and reacting at 10Pa and 200 ℃ for 8 h. Dissolving the obtained product with chloroform, separating out excessive methanol, and vacuum drying the precipitate to obtain the poly D-lactic acid-isopropylidene glucose copolymer. The copolymer is prepared by1H-nuclear magnetic resonance spectrum analysis shows that the molecular chain of the copolymer has a plurality of PDLA segments, the copolymer is not a diblock copolymer, but the number of the PDLA segments cannot be accurately controlled, the weight average relative molecular mass of the copolymer is 38000, and the specific rotation of the copolymer is [ α ]]25 DAbout +145, melting point 152 ℃, crystallinity 58%, water contact angle 79 °.
Advantageous effects
As can be seen from comparative example 1, the molecular weight of the poly D-lactic acid-isopropylidene glucose diblock copolymer is larger than that of PDLA, i.e., the PDLA still has homopolymerization during the copolymerization process, and the molecular weight of the PDLA block is further improved. The poly-D-lactic acid-isopropylidene glucose diblock copolymer has specific optical rotation, melting point and crystallinity similar to PDLA, but the hydrophilicity is improved. As can be seen from comparative example 2, when the molar ratio of IPG to PDLA is less than 4: 1, the poly D-lactic acid-isopropylidene glucose copolymer has a plurality of PDLA segments without forming a diblock structure, and the number of PDLA segments cannot be precisely controlled, so that its melting point, crystallinity and hydrophilicity are greater than those of PDLA, but its hydrophilicity is lower than that of the diblock copolymer. Therefore, the poly D-lactic acid-isopropylidene glucose diblock copolymer prepared by the invention can improve the molecular weight of the polymer, accurately control the molecular chain structure and improve the hydrophilicity of the polylactic acid material.
The above description is only for the purpose of illustrating a few embodiments of the present invention, and should not be taken as limiting the scope of the present invention, in which equivalent changes, modifications, or scaling up or down, etc. made in accordance with the spirit of the present invention should be considered as falling within the scope of the present invention.

Claims (6)

1. A poly D-lactic acid-isopropylidene glucose diblock copolymer material and a preparation method thereof are characterized in that the method comprises the following steps:
(1) preparing 1, 2 by a hydroxyl protection method; 5, 6-O-diisopropylidene glucose
10g of glucose and 200ml of acetone are added into a reactor, stirred and added with proper amount of zinc chloride and phosphoric acid (the mol ratio is 1: 0.1) in sequence, and the mixture reacts for 30 hours at room temperature and normal pressure. Dropwise adding 50% NaOH aqueous solution under rapid stirring, adjusting the pH value of a reaction system to 8.0, performing suction filtration, washing for 2-3 times by using acetone until filtrate is colorless and transparent, performing rotary evaporation on the filtrate, dissolving the obtained solid by using trichloromethane, performing water washing extraction for 2-3 times, performing rotary evaporation on the obtained trichloromethane solution, recrystallizing the obtained sample by using ethyl acetate and petroleum ether for 2-3 times, and obtaining 1, 2 of white needle-shaped crystals; 5, 6-oxo-diisopropylidene glucose.
(2) Preparation of poly D-lactic acid-isopropylidene glucose copolymer
Weighing a certain amount of D-lactic acid, adding the D-lactic acid into a reactor, heating to 150 ℃, reacting for 1 hour under constant temperature at normal pressure, then reducing the pressure to-0.08 MPa, reacting for 4 hours, adding a catalyst, heating to 160-200 ℃, reducing the pressure to complete vacuum, reacting for 4-12 hours to obtain poly D-lactic acid with certain relative molecular mass, and adding 1, 2 with different molar ratios into a reaction system; reacting 5, 6-oxygen-diisopropylidene glucose for 4-12 h under the conditions that the pressure is 10-300 Pa and the temperature is 160-200 ℃. Dissolving the obtained product with chloroform, separating out excessive methanol, and vacuum drying the precipitate to obtain the poly D-lactic acid-isopropylidene glucose copolymer.
2. The poly D-lactic acid-isopropylidene glucose copolymer of claim 1, wherein: the copolymer can also be prepared by the following method: dissolving poly D-lactic acid obtained by melt polymerization with chloroform, precipitating with excessive methanol, and vacuum drying the separated precipitate at 50 deg.C for 10h to obtain purified poly D-lactic acid. Melting purified poly D-lactic acid, and adding 1, 2; 5, 6-oxygen-diisopropylidene glucose and a catalyst are subjected to melt polymerization reaction for 4-12 hours under the conditions that the pressure is 10-300 Pa and the temperature is 160-200 ℃, so that the poly D-lactic acid-isopropylidene glucose copolymer is prepared.
3. The poly D-lactic acid-isopropylidene glucose copolymer of claim 1, wherein: the catalyst is any one of stannous chloride, stannous isooctanoate and p-toluenesulfonic acid, and the dosage of the catalyst is 0.3-0.5 wt% of the total mass of the D-lactic acid.
4. The poly D-lactic acid-isopropylidene glucose copolymer of claim 1, wherein: the 1, 2; when the molar ratio of the 5, 6-O-diisopropylidene glucose to the poly-D-lactic acid is more than 4: 1, a diblock copolymer can be prepared.
5. The poly D-lactic acid-isopropylidene glucose copolymer of claim 1, wherein: the number of the poly D-lactic acid chain segments and the molecular mass can be regulated and controlled by controlling the time of melt polymerization.
6. The poly-D-lactic acid-isopropylidene glucose copolymer according to claim 1, wherein a poly-D-lactic acid-isopropylidene glucose copolymer material having a specific optical rotation [ α ] can be produced according to claim 1]25 DAbout +145, a melting temperature of about 148 ℃, and a crystallinity of about 49%, which are similar to those of poly-D-lactic acid, but have significantly improved hydrophilicity, and the water contact angle of the copolymer is about 72 °.
CN201911353865.5A 2019-12-26 2019-12-26 Poly D-lactic acid-isopropylidene glucose diblock copolymer material and preparation method thereof Pending CN111019109A (en)

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US20030181613A1 (en) * 2002-03-18 2003-09-25 Lele Bhalchandra Shripad Amphiphilic diblock, triblock and star-block copolymers and their pharmaceutical compositions
JP2012031340A (en) * 2010-08-02 2012-02-16 Nihon Univ Stereocomplex and method of producing the same
CN110511358A (en) * 2018-05-22 2019-11-29 南京林业大学 A kind of poly- D-ALPHA-Hydroxypropionic acid glucose copolymer material and its melt polymerization preparation method

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TATSURO OUCHI ET, AL.: "Modification of polylactide upon physical properties by solution-cast blends from polylactide and polylactide-grafted dextran", 《POLYMER》 *
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