CN108559084B - Preparation method of polylactic acid-based hydrophobic film - Google Patents
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Abstract
The invention discloses a preparation method of a polylactic acid-based hydrophobic film, which comprises the following steps: preparing a levorotatory polylactic acid polymer solution into a levorotatory polylactic acid polymer film, rotationally coating a triblock copolymer PDLA-PDMS-PDLA solution on a levorotatory polylactic acid polymer film substrate, and annealing to obtain the polylactic acid base hydrophobic film. The preparation method of the polylactic acid-based hydrophobic film is simple and efficient, the process conditions are easy to control, the uniform hydrophobic film can be prepared, and the preparation method has a high practical application value.
Description
Technical Field
The invention relates to the technical field of films, in particular to a degradable plastic polylactic acid-based film, and particularly relates to a preparation method of a polylactic acid-based hydrophobic film.
Background
At present, the wide use of plastic film products causes serious pollution to the ecological environment, and the main source of the plastic, namely petroleum resources, is in increasing tension. Therefore, the development and use of biodegradable materials are receiving great attention due to many aspects of sustainable use of energy and environmental protection.
Among many biodegradable materials, polylactic acid (PLA) is the most promising, and has the advantages of good compatibility, degradability, mechanical properties, and transparency. Maximum of PLA productIs characterized by being finally degraded into CO in natural environment2And H2O, and thus can be termed a genuine green plastic.
The magnitude of the contact angle of a hydrophobic material surface to a liquid drop is often used to determine wettability, where a solid surface has hydrophobicity when the contact angle θ of the surface to a liquid drop is greater than 90 °, and the wettability of the solid surface is determined by the chemical composition and the microstructure of the surface. Hydrophobic film surfaces have received much attention due to their self-cleaning properties of water-proofing, anti-icing and anti-fouling. However, the prior process for producing the hydrophobic film has the problems of expensive production equipment, severe production conditions, nonbiodegradability and the like. The PLA film solves the problem of biodegradation, and at present, the contact angle of a common polylactic acid film is 70-80 degrees, and the film has no hydrophobicity and weak self-cleaning capability.
Disclosure of Invention
The invention aims to provide a preparation method of a polylactic acid-based hydrophobic film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a polylactic acid-based hydrophobic film, which comprises the following steps:
preparing a levorotatory polylactic acid (PLLA) polymer solution into a levorotatory polylactic acid polymer film, spin-coating a triblock copolymer PDLA-PDMS-PDLA solution on the levorotatory polylactic acid polymer film substrate, and annealing to obtain the polylactic acid-based hydrophobic film.
The preparation method of the polylactic acid-based hydrophobic film also comprises the step of annealing the levorotatory polylactic acid polymer film.
The poly-L-lactic acid (PLLA) polymer solution is prepared by dissolving poly-L-lactic acid in an organic solvent, wherein the concentration of poly-L-lactic acid is 1-200 mg/ml, and preferably 100 mg/ml.
The triblock copolymer PDLA-PDMS-PDLA solution is prepared by dissolving a triblock copolymer PDLA-PDMS-PDLA in an organic solvent, wherein the concentration is 1-200 mg/ml, and preferably 100 mg/ml.
The organic solvent is at least one of dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane and a mixed solution of tetrahydrofuran and dichloromethane, preferably dichloromethane and tetrahydrofuran, wherein dichloromethane is used for dissolving PLLA polymer, and tetrahydrofuran is used for dissolving triblock copolymer PDLA-PDMS-PDLA.
The annealing treatment is carried out for 10-60 min under the condition that the temperature is 80-180 ℃, the preferred temperature is 100 ℃, and the time is 30 min.
The number average molecular weight of the poly-L-lactic acid (PLLA) polymer is 10000-80000, preferably 73499.
The number average molecular weight of the triblock copolymer PDLA-PDMS-PDLA is 10000-170000, preferably 141350.
The preparation method of the poly-L-lactic acid (PLLA) polymer comprises the following steps:
weighing purified L-lactide, an initiator, a catalyst and a solvent in an anhydrous, oxygen-free and dust-free environment, reacting for 1-24 h at the temperature of 110-150 ℃, adding cold ether for precipitation, and vacuumizing to obtain the poly (L-lactide) (PLLA) polymer.
The mass ratio of the initiator to the L-lactide is (1-2) to 1000, and preferably 1.3 to 1000.
The mass ratio of the catalyst to the L-lactide is (1-10): 1000, and preferably 5: 1000.
The concentration of the L-lactide dissolved in the solvent is 0.25-0.5 g/ml, and preferably 0.33 g/ml.
The initiator is methyl lactate, lactic acid and lauryl alcohol, and preferably methyl lactate.
The catalyst is stannous octoate and zinc oxide, preferably stannous octoate, the stannous octoate is efficient and has good compatibility with a reaction system, and the phenomena of coking and discoloration can be obviously reduced.
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane and cyclohexane.
The preparation method of the triblock copolymer PDLA-PDMS-PDLA comprises the following steps:
weighing purified D-lactide, an initiator, a catalyst and a solvent in an anhydrous, oxygen-free and dust-free environment, reacting for 1-24 h at the temperature of 110-150 ℃, adding cold ether for precipitation, and vacuumizing to obtain the triblock copolymer PDLA-PDMS-PDLA.
The mass ratio of the initiator to the D-lactide is (0.01-0.8): 1, and preferably (0.03-0.5): 1.
The mass ratio of the catalyst to the D-lactide is (1-10): 1000, and preferably (3-5): 1000.
The concentration of the D-lactide dissolved in the solvent is 0.1-0.5 g/ml, and preferably 0.2-0.3 g/ml.
The initiator is Mn10000, 4500-5500, 600-850 Polydimethylsiloxane (PDMS), preferably Mn＝10000。
The catalyst is stannous octoate and zinc oxide, preferably stannous octoate, the stannous octoate is efficient and has good compatibility with a reaction system, and the phenomena of coking and discoloration can be obviously reduced.
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane and cyclohexane.
The L-lactide or D-lactide is purified, and the purification comprises the following steps:
mixing L-lactide or D-lactide with ethyl acetate with the mass ratio of 75%, completely dissolving the L-lactide or D-lactide at the temperature of 50-80 ℃, cooling at room temperature, placing in a refrigerator for storage overnight, carrying out suction filtration on the ethyl acetate with impurities dissolved, purifying for three times according to the method, finally vacuumizing the L-lactide or D-lactide, and removing all solvents to obtain the purified L-lactide or D-lactide.
PDLA in PDLA-PDMS-PDLA is poly (D-lactic acid).
The structural formula of the lactide (DL-lactide) is as follows:
the reaction equation for PLLA polymer synthesis is shown below:
and (3) synthesis of an initiator:
first monomer addition:
chain growth:
chain transfer:
the polymerization degree n is approximately equal to 139-1112.
The polymerization degree n is the number average molecular weight of polylactic acid/the molecular weight of polylactic acid repeating unit (72),
Mnn ≈ 1020 of PLLA of 73499.
The reaction equation for the synthesis of the triblock copolymer PDLA-PDMS-PDLA is shown below:
m is approximately equal to 135 (PDMS with the number average molecular weight of 10000), n is approximately equal to 1-972 (M)n141350 PDLA-PDMS-PDLA with m ≈ 135, n ≈ 912).
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the preparation method of the polylactic acid-based hydrophobic film is characterized in that the polylactic acid-based hydrophobic film is prepared from a biodegradable material polylactic acid, the levorotatory polylactic acid (PLLA) film and the triblock polymer PDLA-PDMS-PDLA film are enabled to act through the stereocomplex action of the polylactic acid, and due to the fact that silicon with low surface free energy in Polydimethylsiloxane (PDMS) and the PLLA polymer and the block PDLA have the stereocomplex action to generate the dual action of surface micro-morphology, the polylactic acid-based hydrophobic film has the hydrophobic characteristic.
The preparation method of the polylactic acid-based hydrophobic film comprises the steps of reacting a PLLA film matrix with a PDLA-PDMS-PDLA triblock copolymer film through a stereo composite effect to prepare the polylactic acid-based hydrophobic film, and performing the stereo composite effect on the PLLA film and the PDLA-PDMS-PDLA triblock copolymer film to prepare the polylactic acid-based hydrophobic film.
Drawings
FIG. 1 is a field emission scanning electron microscope image of a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA polymer solution with a molecular weight of 73499 and a tetrahydrofuran triblock copolymer PDLA-PDMS-PDLA solution with a molecular weight of 141350 and a concentration of 100 mg/ml.
FIG. 2 is a SEM image of the field emission of polylactic acid-based hydrophobic film (not annealed) formed by PLLA polymer solution with molecular weight of 73499 and PDLA-PDMS-PDLA solution with molecular weight of 141350 and concentration of 100 mg/ml.
FIG. 3 is an X-ray diffraction pattern of a polylactic acid-based hydrophobic film, wherein a is an X-ray diffraction pattern of a film formed from a PLLA (molecular weight 73499) polymer solution annealed at 100 ℃ for 30min, b is an X-ray diffraction pattern of a film formed from a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution annealed at 100 ℃ for 30min, c is an X-ray diffraction pattern of a polylactic acid-based hydrophobic film formed from a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution annealed at 100 ℃ for 30min, sc represents a stereocomplex crystal, and hc represents a homogeneous crystal.
Fig. 4 is a graph of contact angle for a polylactic acid-based hydrophobic film, where a is PLLA (molecular weight 73499) polymer film (unannealed) with a contact angle of 85.5 °; b is PLLA (molecular weight 73499) polymer film (annealed at 100 ℃ for 30min) with a contact angle of 58 °; c is a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) film (annealed at 100 ℃ for 30min) with a contact angle of 95.49 °; d is a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 21036), and the contact angle is 126 degrees; e is a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350), and the contact angle is 138.25 degrees; f is polylactic acid-based hydrophobic film (annealed at 180 ℃ for 30min) formed by PLLA (molecular weight 73499) polymer solution and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution, and the contact angle is 125.75 degrees.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents and starting materials used in the present invention are commercially available or can be prepared according to literature procedures. Unless otherwise indicated, percentages and parts are by weight.
The reagents and materials used in the examples of the invention were as follows:
l-lactide, medical grade, Corbion-Purac; d-lactide, medical grade, Corbion-Purac; methyl lactate, analytical grade, Adamas Reagent Co, ltd; stannous octoate, analytical grade, Adamas Reagent Co, ltd; PDMS (M)n＝10000)，DMS-C23，GELEST，INC；PDMS(Mn＝4500-5500)，DMS-C21，GELEST，INC；PDMS(Mn650 + 850), DMS-C16, GELEST, INC; toluene, analytically pure, Shanghai Vocko Biotech limited; anhydrous ether, analytical grade, shanghai tatatake technolog gmbh.
The preparation method of the polylactic acid-based hydrophobic film firstly synthesizes a triblock copolymer (PDLA-PDMS-PDLA) of levorotatory polylactic acid (PLLA), dextrorotatory polylactic acid and polydimethylsiloxane. Dissolving PLLA in an organic solvent, spin-coating on a glass slide to prepare a PLLA polymer film, carrying out certain annealing treatment, then spin-coating an organic solvent of a triblock copolymer PDLA-PDMS-PDLA on the PLLA polymer film, and carrying out certain annealing treatment to obtain the polylactic acid-based hydrophobic film.
According to the preparation method of the polylactic acid-based hydrophobic film, the isomer PDLA of the PLLA polymer and PDMS with certain hydrophobicity are adopted to form the triblock copolymer PDLA-PDMS-PDLA, and then the triblock copolymer PDLA-PDMS-PDLA film is prepared on the surface of a PLLA polymer film matrix with relatively high molecular weight. The polylactic acid-based hydrophobic film is prepared through the combined action of silicon with low surface free energy in a block and a surface microstructure formed by the stereo composite action of a matrix PLLA polymer and PDLA in the block polymer.
The initiator methyl lactate is a solution with the concentration of 50mg/ml prepared by using anhydrous toluene, and the catalyst stannous octoate is a solution with the concentration of 50mg/ml prepared by using anhydrous toluene.
Example 1
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing the materials in a glove box, adding 10g L-lactide, 260ul methyl lactate, 1ml stannous octoate and 30ml solvent toluene in a three-neck flask, taking out the materials from the glove box, and placing the materials in an oil bath kettle at 130 ℃ for reaction for 3-5 hours. Adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24h, and removing all solvents to obtain a PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 200g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
The materials were weighed in a glove box, and 8.28g D-lactide and 0.3g PDMS (M) were added to a three-necked flaskn10000), 500ul stannous octoate and 30ml solvent toluene, taking out from a glove box, placing in an oil bath kettle at 130 ℃ for reaction for 3-5 h, adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24h, and removing all solvents to obtain the triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 141350.
Preparation of PLLA Polymer and triblock copolymer PDLA-PDMS-PDLA solution
A PLLA polymer powder (1 g) was weighed out and dissolved in methylene chloride to prepare a PLLA solution having a concentration of 100 mg/ml. Weighing 1g of triblock copolymer PDLA-PDMS-PDLA powder, and respectively preparing triblock copolymer PDLA-PDMS-PDLA solutions with the concentrations of 10mg/ml, 50mg/ml and 100mg/ml by using dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane with the mass ratio of 1:4 and a mixed solution of tetrahydrofuran and dichloromethane with the mass ratio of 1: 4.
Preparation of PLLA Polymer films
And (3) spin-coating the PLLA solution with the concentration of 100mg/ml on a glass slide by a spin coater at the spin-coating speed of 6000r/min, and performing normal-temperature storage and 100-DEG annealing for 30min to obtain the PLLA polymer film with the contact angle of 50-90 degrees.
Preparation of triblock copolymer PDLA-PDMS-PDLA film
The triblock copolymer PDLA-PDMS-PDLA solution with different concentrations (10mg/ml, 50mg/ml and 100mg/ml) and different solvents (dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane with a mass ratio of 1:4 and a mixed solution of tetrahydrofuran and dichloromethane with a mass ratio of 1: 4) is coated on a glass slide by a spin coater in a spin coating speed of 6000r/min, and the triblock copolymer PDLA-PDMS-PDLA film with a contact angle of 90-110 degrees is obtained after the processes of normal temperature preservation and 100 ℃ annealing for 30 min.
Preparation of polylactic acid-based hydrophobic film
And spin-coating the PLLA solution with the concentration of 100mg/ml on a glass slide by using a spin coater at the spin-coating speed of 6000r/min, spin-coating a triblock copolymer PDLA-PDMS-PDLA solution with the concentration of 100mg/ml and a solvent of tetrahydrofuran on a PLLA polymer film substrate, annealing at 100 ℃ for 30min, and storing at normal temperature. And carrying out field emission Scanning Electron Microscope (SEM), X-ray diffraction (XRD) and contact angle test on the obtained polylactic acid-based hydrophobic film.
From XRD results, obvious stereo complex crystal peaks appear, and the contact angle test result is 110-130 degrees. FIG. 1 is a field emission SEM image of a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA polymer solution with a molecular weight of 73499 and a PDLA-PDMS-PDLA solution with a molecular weight of 141350 and a concentration of 100 mg/ml. As can be seen from the figure, multilayer three-dimensional holes of 0.5-4.3 um appear, XRD results show that obvious stereo composite crystals appear, the stereo composite crystals are more compact in structure than homogeneous polylactic acid crystals, and chain segments are shrunk due to the compact structure, so that the multilayer three-dimensional hole appearance is formed.
X-ray diffraction As shown in FIG. 3, FIG. 3 is an X-ray diffraction pattern of a polylactic acid-based hydrophobic film, wherein a is an X-ray diffraction pattern of a film formed from a PLLA (molecular weight 73499) polymer solution annealed at 100 ℃ for 30min, b is an X-ray diffraction pattern of a film formed from a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution annealed at 100 ℃ for 30min, c is an X-ray diffraction pattern of a polylactic acid-based hydrophobic film formed from a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution annealed at 100 ℃ for 30min, sc represents a stereocomplex crystal, and hc represents a homogeneous crystal. As can be seen from the figure, the annealed polylactic acid-based hydrophobic film shows stereocomplex crystals, and the diffraction peaks at 2 θ ═ 11.9 °, 20.7 ° and 23.9 ° are respectively assigned to the diffraction peaks of the crystal planes of the stereocomplex crystals with miller indices (110), (300)/(030) and (220).
Contact angle test results are shown in fig. 4, fig. 4 is a contact angle graph of a polylactic acid-based hydrophobic film, wherein a is a PLLA (molecular weight 73499) polymer film (not annealed), and the contact angle is 85.5 °; b is PLLA (molecular weight 73499) polymer film (annealed at 100 ℃ for 30min) with a contact angle of 58 °; c is a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) film (annealed at 100 ℃ for 30min) with a contact angle of 95.49 °; d is a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 21036), and the contact angle is 126 degrees; e is a polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) formed by a PLLA (molecular weight 73499) polymer solution and a triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350), and the contact angle is 138.25 degrees; f is polylactic acid-based hydrophobic film (annealed at 180 ℃ for 30min) formed by PLLA (molecular weight 73499) polymer solution and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution, and the contact angle is 125.75 degrees. Compared with the annealed pure PLLA polymer film and the non-annealed pure PLLA polymer film, the contact angles of the annealed polylactic acid-based hydrophobic film are respectively improved by nearly 80 degrees and 53 degrees, which shows that the polylactic acid-based hydrophobic film can be prepared by adding silicon containing low surface free energy on the surface for chemical modification and under the combined action of the rough surface appearance generated by stereo composition.
Example 2
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing the materials in a glove box, adding 10g L-lactide, 260ul methyl lactate, 1ml stannous octoate and 30ml solvent toluene in a three-neck flask, taking out the materials from the glove box, and placing the materials in an oil bath kettle at 130 ℃ for reaction for 3-5 hours. Adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24h, and removing all solvents to obtain a PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 200g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
The materials were weighed in a glove box, and 8.28g D-lactide and 0.3g PDMS (M) were added to a three-necked flaskn10000), 500ul stannous octoate and 30ml solvent toluene, taking out from a glove box, placing in an oil bath kettle at 130 ℃ for reaction for 3-5 h, adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24h, and removing all solvents to obtain the triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 141350.
Preparation of PLLA Polymer and triblock copolymer PDLA-PDMS-PDLA solution
A PLLA polymer powder (1 g) was weighed out and dissolved in methylene chloride to prepare a PLLA solution having a concentration of 100 mg/ml. Weighing 1g of triblock copolymer PDLA-PDMS-PDLA powder, and respectively preparing triblock copolymer PDLA-PDMS-PDLA solutions with the concentrations of 10mg/ml, 50mg/ml and 100mg/ml by using dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane with the mass ratio of 1:4 and a mixed solution of tetrahydrofuran and dichloromethane with the mass ratio of 1: 4.
Preparation of polylactic acid-based hydrophobic film
And spin-coating the PLLA solution with the concentration of 100mg/ml on a glass slide by using a spin coater at the spin-coating speed of 6000r/min, annealing for 30min at 100 ℃, spin-coating a triblock copolymer PDLA-PDMS-PDLA solution with the concentration of 100mg/ml and a solvent of tetrahydrofuran on a PLLA polymer film substrate, annealing for 30min at 100 ℃, and storing at normal temperature. And carrying out field emission Scanning Electron Microscope (SEM), X-ray diffraction (XRD) and contact angle test on the obtained polylactic acid-based hydrophobic film. From XRD results, obvious stereo complex crystal peaks appear, and the contact angle test result is 110-140 degrees.
Example 3
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing materials in a glove box, adding 5g of L-lactide, 130ul of methyl lactate (the methyl lactate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml), 500ul of stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml) and 15ml of solvent toluene into a three-neck flask, taking out the mixture from the glove box, placing the mixture in an oil bath kettle at 130 ℃ for reaction for 5 hours, adding 60ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24 hours, and removing all solvents to obtain the PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 20g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
The materials were weighed in a glove box, and 8.28g of D-lactide and PDMS (M) were added to a three-necked flaskn＝10000)0.3g, 828ul stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and having the concentration of 50 mg/ml) and 30ml of solvent toluene, taking out the stannous octoate from a glove box, placing the stannous octoate in an oil bath kettle at 130 ℃ for reaction for 5 hours, adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24 hours, and removing all solvents to obtain the triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 141350.
Preparation of polylactic acid-based hydrophobic film
And (3) spin-coating the PLLA solution (the solvent is dichloromethane) with the concentration of 100mg/ml on a glass slide by using a spin coater at the spin-coating speed of 6000r/min, spin-coating a triblock copolymer PDLA-PDMS-PDLA solution with the concentration of 100mg/ml and tetrahydrofuran as the solvent on a PLLA polymer film substrate, annealing at 100 ℃ for 30min, and storing at normal temperature. The obtained polylactic acid-based hydrophobic film is subjected to field emission Scanning Electron Microscope (SEM), X-ray diffraction (XRD) and contact angle tests, and the annealed polylactic acid-based hydrophobic film has a plurality of three-dimensional holes obviously larger than that of the unannealed polylactic acid-based hydrophobic film as can be seen by the SEM, and the appearance of the three-dimensional composition can generate great influence on the surface appearance of the film by combining with XRD. The contact angle of the PLLA polymer film was 85.5 °, which decreased to 58 ° after annealing at 100 ℃ for 30min, the contact angle of the triblock copolymer PDLA-PDMS-PDLA film (annealed at 100 ℃ for 30min) was 95.49 °, and the contact angle of the final polylactic acid-based hydrophobic film (annealed at 100 ℃ for 30min) was 138.25 °. Compared with the annealed PLLA polymer film, the contact angle of the annealed polylactic acid-based hydrophobic film is improved by nearly 80 degrees.
Example 4
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing materials in a glove box, adding 5g of L-lactide, 130ul of methyl lactate (the methyl lactate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml), 500ul of stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml) and 15ml of solvent toluene into a three-neck flask, taking out the mixture from the glove box, placing the mixture in an oil bath kettle at 130 ℃ for reaction for 5 hours, adding 60ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24 hours, and removing all solvents to obtain the PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 20g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing in a glove box, adding 5g of D-lactide and PDMS (M) into a three-neck flaskn10000)2.5g, 500ul stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml) and 20ml of solvent toluene, the mixture is taken out from a glove box and placed in an oil bath kettle at 130 ℃ for reaction for 4 hours, 60ml of anhydrous ether stored in a refrigerator is added for precipitation, finally, the reaction solution is placed in a cold trap device for vacuumizing for 24 hours, and all the solvent is removed to obtain the triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 21036.
Preparation of polylactic acid-based hydrophobic film
The PLLA solution (solvent is dichloromethane) with the concentration of 100mg/ml is spin-coated on a glass slide by a spin coater at the spin-coating speed of 6000r/min, then a triblock copolymer PDLA-PDMS-PDLA (molecular weight of 21036) solution with the concentration of 100mg/ml and tetrahydrofuran as a solvent is spin-coated on a PLLA polymer film substrate, and the solution is annealed at 100 ℃ for 30min and then stored at normal temperature. The contact angle of the final polylactic acid-based hydrophobic film (annealed at 100 ℃ C. for 30min) was 125.99 degrees, and the polylactic acid-based hydrophobic film prepared in this example was slightly less hydrophobic than the polylactic acid-based hydrophobic film prepared in example 3 because it was easier to form a stereocomplex crystal when the segment lengths of PLLA and PDLA were similar. The polymerization degree of PLLA and PDLA in example 3 was 1020 and 912, respectively; the polymerization degree of PLLA and PDLA in this example was 1020 and 77, respectively.
Comparative example 1
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing the materials in a glove box, adding 10g L-lactide, 260ul methyl lactate, 1ml stannous octoate and 30ml solvent toluene in a three-neck flask, taking out the materials from the glove box, and placing the materials in an oil bath kettle at 130 ℃ for reaction for 3-5 hours. Adding 100ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24h, and removing all solvents to obtain a PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 200g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
The materials were weighed in a glove box, and 8.28g D-lactide and 0.3g PDMS (M) were added to a three-necked flaskn10000), 500ul stannous octoate and 30ml solvent toluene, taking out from the glove box, placing in an oil bath kettle at 130 ℃ for reaction for 3-5 h, adding 100ml anhydrous ether stored in a refrigerator for precipitation, and finally, adding the solvent toluene into the glove boxAnd putting the reaction liquid in a cold trap device, vacuumizing for 24h, and removing all solvents to obtain a triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 141350.
Preparation of PLLA Polymer and triblock copolymer PDLA-PDMS-PDLA solution
A PLLA polymer powder (1 g) was weighed out and dissolved in methylene chloride to prepare a PLLA solution having a concentration of 100 mg/ml. Weighing 1g of triblock copolymer PDLA-PDMS-PDLA powder, and respectively preparing triblock copolymer PDLA-PDMS-PDLA solutions with the concentrations of 10mg/ml, 50mg/ml and 100mg/ml by using dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane with the mass ratio of 1:4 and a mixed solution of tetrahydrofuran and dichloromethane with the mass ratio of 1: 4.
Preparation of PLLA Polymer films
And (3) spin-coating the PLLA solution with the concentration of 100mg/ml on a glass slide by a spin coater at the spin-coating speed of 6000r/min, and performing normal-temperature storage and 100-DEG annealing for 30min to obtain the PLLA polymer film with the contact angle of 50-90 degrees.
Preparation of triblock copolymer PDLA-PDMS-PDLA film
The triblock copolymer PDLA-PDMS-PDLA solution with different concentrations (10mg/ml, 50mg/ml and 100mg/ml) and different solvents (dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane with a mass ratio of 1:4 and a mixed solution of tetrahydrofuran and dichloromethane with a mass ratio of 1: 4) is coated on a glass slide by a spin coater in a spin coating speed of 6000r/min, and the triblock copolymer PDLA-PDMS-PDLA film with a contact angle of 90-110 degrees is obtained after the processes of normal temperature preservation and 100 ℃ annealing for 30 min.
Preparation of polylactic acid-based hydrophobic film
And (3) spin-coating the PLLA solution with the concentration of 100mg/ml on a glass slide by using a spin coater at the spin-coating speed of 6000r/min, spin-coating a triblock copolymer PDLA-PDMS-PDLA solution with the concentration of 100mg/ml and a solvent of tetrahydrofuran on a PLLA polymer film substrate, and performing field emission Scanning Electron Microscope (SEM), X-ray diffraction (XRD) and contact angle test on the obtained polylactic acid-based hydrophobic film after normal-temperature storage.
From XRD results, weak stereo complex crystal peaks appear, and the contact angle test result is 100-115 degrees. FIG. 2 shows a field emission SEM image of a polylactic acid-based hydrophobic film (not annealed) formed by a PLLA polymer solution with a molecular weight of 73499 and a tetrahydrofuran triblock copolymer PDLA-PDMS-PDLA solution with a molecular weight of 141350 and a concentration of 100 mg/ml. As can be seen from the figure, pores of 1.5um to 5.5um are present, which are formed by volatilization of the solvent. The figure shows no other special micro-topography, which indicates that the hydrophobicity of the unannealed polylactic acid-based hydrophobic film is improved compared with a pure PLLA polymer film because the triblock copolymer PDLA-PDMS-PDLA contains silicon with low surface free energy.
Comparative example 2
Synthesis of PLLA polymers
Purification of L-lactide: purifying L-lactide with ethyl acetate for 3 times, mixing 200g L-lactide with 75% ethyl acetate, dissolving L-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
Weighing materials in a glove box, adding 5g of L-lactide, 130ul of methyl lactate (the methyl lactate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml), 500ul of stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml) and 15ml of solvent toluene into a three-neck flask, taking out the mixture from the glove box, placing the mixture in an oil bath kettle at 130 ℃ for reaction for 5 hours, adding 60ml of anhydrous ether stored in a refrigerator for precipitation, finally placing the reaction liquid in a cold trap device for vacuumizing for 24 hours, and removing all solvents to obtain the PLLA polymer with the molecular weight of 73499.
Synthesis of triblock copolymer PDLA-PDMS-PDLA
Purification of D-lactide: purifying D-lactide with ethyl acetate for 3 times, mixing 20g D-lactide with 75% ethyl acetate, dissolving D-lactide completely in water bath at 60 deg.C, cooling at room temperature, standing in refrigerator overnight, filtering to remove impurity-dissolved ethyl acetate, purifying for three times, and vacuumizing in cold trap for 24 hr to remove all solvent.
The materials were weighed in a glove box, and 8.28g of D-lactide and PDMS (M) were added to a three-necked flaskn10000), 828ul of stannous octoate (the stannous octoate is a solution prepared by anhydrous toluene and has the concentration of 50 mg/ml) and 30ml of solvent toluene, the mixture is taken out from a glove box and placed in an oil bath kettle at the temperature of 130 ℃ for reaction for 5 hours, 100ml of anhydrous ether stored in a refrigerator is added for precipitation, finally, the reaction solution is placed in a cold trap device for vacuumizing for 24 hours, and all the solvent is removed, so that the triblock copolymer PDLA-PDMS-PDLA with the molecular weight of 141350 is obtained.
Preparation of polylactic acid-based hydrophobic film
The PLLA solution (solvent is dichloromethane) with the concentration of 100mg/ml and the molecular weight of 73499 is spin-coated on a glass slide by a spin coater at the spin-coating speed of 6000r/min, then a triblock copolymer PDLA-PDMS-PDLA (molecular weight of 141350) solution with the concentration of 100mg/ml and tetrahydrofuran is spin-coated on a PLLA polymer film matrix, and the solution is annealed at 180 ℃ for 30min and then stored at normal temperature. The contact angle of the final polylactic acid-based hydrophobic film (annealed at 180 ℃ for 30min) was 125.75 °. The polylactic acid-based hydrophobic film prepared in this example has poor hydrophobicity compared with the polylactic acid-based hydrophobic film prepared in example 3, because the melting temperature of the polylactic acid is 180 ℃, and the microscopic morphology of the polylactic acid-based surface is damaged due to the excessively high temperature, which results in the decrease of the hydrophobicity.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a polylactic acid-based hydrophobic film mainly comprises the following steps:
preparing a levorotatory polylactic acid polymer solution into a levorotatory polylactic acid polymer film, rotationally coating a triblock copolymer PDLA-PDMS-PDLA solution on a levorotatory polylactic acid polymer film substrate, and annealing to obtain a target object;
wherein the number average molecular weight of the L-polylactic acid polymer is 10,000-80,000, the number average molecular weight of the triblock copolymer PDLA-PDMS-PDLA is 10,000-170,000, and the polymerization degree of the L-polylactic acid polymer and the polymerization degree of PDLA in the triblock copolymer PDLA-PDMS-PDLA are 1020 and 912 respectively; the annealing treatment is carried out at the temperature of 100 ℃ for 30 minutes;
the PDLA is dextrorotatory polylactic acid, and the PDMS is polydimethylsiloxane.
2. The method according to claim 1, further comprising a step of subjecting the L-polylactic acid polymer film to an annealing treatment.
3. The method according to claim 1, wherein the L-polylactic acid polymer solution is prepared by dissolving L-polylactic acid in an organic solvent at a concentration of 1mg/ml to 200 mg/ml; the triblock copolymer PDLA-PDMS-PDLA solution is prepared by dissolving a triblock copolymer PDLA-PDMS-PDLA in an organic solvent, wherein the concentration is 1 mg/ml-200 mg/ml.
4. The method according to claim 3, wherein the organic solvent is selected from the group consisting of: at least one of dichloromethane, tetrahydrofuran, dimethylformamide, a mixed solution of tetrahydrofuran and n-hexane, or a mixed solution of tetrahydrofuran and dichloromethane.
5. The production method according to any one of claims 1 to 3, wherein the method for producing the L-polylactic acid polymer used comprises the steps of:
weighing purified L-lactide, an initiator, a catalyst and a solvent in an anhydrous, oxygen-free and dust-free environment, reacting for 1-24 h at the temperature of 110-150 ℃, adding cold ether for precipitation, and vacuumizing to obtain the target L-polylactic acid polymer;
wherein the mass ratio of the initiator to the L-lactide is (1-2): 1000, the mass ratio of the catalyst to the L-lactide is (1-10): 1000, and the concentration of the L-lactide dissolved in the solvent is 0.25 g/ml-0.5 g/ml.
6. The method according to claim 5, wherein the initiator is methyl lactate, lactic acid or lauryl alcohol, the catalyst is stannous octoate or zinc oxide, and the solvent is selected from the group consisting of: at least one of toluene, tetrahydrofuran, dichloromethane, or cyclohexane.
7. The method of claim 5, wherein purifying the L-lactide comprises the steps of:
mixing L-lactide with ethyl acetate with the mass ratio of 75%, completely dissolving the L-lactide at the temperature of 50-80 ℃, cooling at room temperature, placing in a refrigerator for storage overnight, and filtering the ethyl acetate with impurities dissolved completely;
purifying for three times according to the method, finally vacuumizing the L-lactide, and removing all solvents to obtain the purified L-lactide.
8. The method according to any one of claims 1 to 3, wherein the method for preparing the triblock copolymer PDLA-PDMS-PDLA comprises the following steps:
weighing purified D-lactide, an initiator, a catalyst and a solvent in an anhydrous, oxygen-free and dust-free environment, reacting for 1-24 h at the temperature of 110-150 ℃, adding cold ether for precipitation, and vacuumizing to obtain a target triblock copolymer;
wherein the mass ratio of the initiator to the D-lactide is (0.01-0.8): 1, the mass ratio of the catalyst to the D-lactide is (1-10): 1000, and the concentration of the D-lactide dissolved in the solvent is 0.1-0.5 g/ml.
9. The method of claim 8, wherein the initiator is Mn10000 of polydimethylsiloxane, wherein the catalyst is stannous octoate or zinc oxide, and the solvent is selected from the following components: is at least one of toluene, tetrahydrofuran, dichloromethane or cyclohexane.
10. The method of claim 8, wherein purifying the D-lactide comprises the steps of:
mixing D-lactide with 75% ethyl acetate by mass ratio, completely dissolving the D-lactide at the temperature of 50-80 ℃, cooling at room temperature, placing in a refrigerator for storage overnight, and filtering the ethyl acetate dissolved with impurities;
purifying for three times according to the method, finally vacuumizing the D-lactide, and removing all solvents to obtain the purified D-lactide.
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| CN109880327A (en) * | 2019-03-07 | 2019-06-14 | 华东理工大学 | A kind of poly (lactic acid) composition, its self-assembly and preparation method |
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| CN114504954B (en) * | 2020-11-16 | 2023-03-28 | 中国石油化工股份有限公司 | Multilayer super-hydrophobic composite membrane and preparation method thereof |
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