CN108559084A - A kind of preparation method of polylactic acid base hydrophobic film - Google Patents
A kind of preparation method of polylactic acid base hydrophobic film Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of polylactic acid base hydrophobic film, include the following steps：L-lactic acid thin polymer film is made in l-lactic acid polymer solution, triblock copolymer PDLA PDMS PDLA solution is spun on above-mentioned l-lactic acid thin polymer film matrix, by annealing, obtains the polylactic acid base hydrophobic film.The preparation method of the polylactic acid base hydrophobic film of the present invention is simple and efficient, and easy control of process conditions can prepare uniform hydrophobic film, has larger actual application value.
Description
Technical field
The present invention relates to thin film technique fields, specifically, being related to a kind of degradation plastic polylactic acid base film, especially relate to
And a kind of preparation method of polylactic acid base hydrophobic film.
Background technology
Currently, being widely used for plastic membrane product causes serious pollution to ecological environment, and plastics is main
Source petroleum resources also be becoming tight by day.Therefore, various considerations such as the sustainable use based on the energy and environmental protection, exploitation
With use Biodegradable material to be now subjected to prodigious concern.
In numerous biodegradable materials, polylactic acid (PLA) is most promising, with good phase
The advantages that capacitive, degradation property, mechanical performance and transparency.The maximum characteristic of PLA products is can be final in bad border naturally
It is degraded to CO2And H2O, therefore qualified green plastic can be deserved to be called.
Hydrophobic material surface is often used to judgement wetability to the contact angle size of drop, when surface is to the contact angle of drop
When θ is more than 90 °, the surface of solids just has hydrophobicity, the wetability of the surface of solids common by chemical composition and surface microstructure
It determines.Hydrophobic film surface due to waterproof, the anti-freeze and automatically cleanings property such as anti-pollution and have received widespread attention.But
The problems such as to be that there are production equipments during producing hydrophobic film at present expensive, working condition is not harsh, biodegradable.PLA
Film solve the problems, such as it is biodegradable this, currently, the contact angle of common polylactic acid film is 70 ° -80 °, such film does not have
There are hydrophobicity, automatical cleaning ability weak.
Invention content
The object of the present invention is to provide a kind of preparation methods of polylactic acid base hydrophobic film.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
The present invention provides a kind of preparation methods of polylactic acid base hydrophobic film, include the following steps：
L-lactic acid thin polymer film is made in l-lactic acid (PLLA) polymer solution, by triblock copolymer
PDLA-PDMS-PDLA solution is spun on above-mentioned l-lactic acid thin polymer film matrix, by annealing, obtains institute
State polylactic acid base hydrophobic film.
The preparation method of the polylactic acid base hydrophobic film further includes l-lactic acid thin polymer film by annealing.
L-lactic acid (PLLA) polymer solution is that l-lactic acid is dissolved in organic solvent, a concentration of 1~
200mg/ml, preferably 100mg/ml.
The triblock copolymer PDLA-PDMS-PDLA solution is to be dissolved in triblock copolymer PDLA-PDMS-PDLA
In organic solvent, a concentration of 1~200mg/ml, preferably 100mg/ml.
The organic solvent is that the mixing of dichloromethane, tetrahydrofuran, dimethylformamide, tetrahydrofuran and n-hexane is molten
At least one of the mixed solution of liquid, tetrahydrofuran and dichloromethane, preferably dichloromethane, tetrahydrofuran, dichloromethane
For dissolving PLLA polymer, tetrahydrofuran is for dissolving triblock copolymer PDLA-PDMS-PDLA.
The annealing is the 10~60min that anneals under conditions of temperature is 80~180 DEG C, and preferred temperature is 100
DEG C, time 30min.
The number-average molecular weight of 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 l-lactic acid (PLLA) polymer includes the following steps：
In anhydrous, anaerobic, dustless environment, L- lactides, initiator, catalysts and solvents after purification are weighed, in temperature
Degree is reaction 1 under conditions of 110~150 DEG C~for 24 hours, and cold ether is added and is precipitated, is obtained after vacuumizing described left-handed poly-
Lactic acid (PLLA) polymer.
The mass ratio of the initiator and L- lactides is (1~2):1000, preferably 1.3:1000.
The mass ratio of the catalyst and L- lactides is (1~10):1000, preferably 5:1000.
The L- lactides are dissolved in a concentration of 0.25~0.5g/ml of solvent, preferably 0.33g/ml.
The initiator is methyl lactate, lactic acid, laruyl alcohol, preferably methyl lactate.
The catalyst is stannous octoate, zinc oxide, preferably stannous octoate, and stannous octoate is efficient, with reaction system phase
Capacitive is good, can significantly reduce coking, metachromatism.
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane, hexamethylene.
The preparation method of the triblock copolymer PDLA-PDMS-PDLA includes the following steps：
In anhydrous, anaerobic, dustless environment, D- lactides, initiator, catalysts and solvents after purification are weighed, in temperature
Degree is reaction 1 under conditions of 110~150 DEG C~for 24 hours, and cold ether is added and is precipitated, the three block is obtained after vacuumizing
Copolymer p DLA-PDMS-PDLA.
The mass ratio of the initiator and D- lactides is (0.01~0.8):1, preferably (0.03~0.5):1.
The mass ratio of the catalyst and D- lactides is (1~10):1000, preferably (3~5):1000.
The D- lactides are dissolved in a concentration of 0.1~0.5g/ml of solvent, preferably 0.2~0.3g/ml.
The initiator is Mn=10000,4500~5500,600~850 dimethyl silicone polymer (PDMS), preferably Mn
=10000.
The catalyst is stannous octoate, zinc oxide, preferably stannous octoate, and stannous octoate is efficient, with reaction system phase
Capacitive is good, can significantly reduce coking, metachromatism.
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane, hexamethylene.
By purifying, purifying includes the following steps for the L- lactides or D- lactides：
L- lactides or D- lactides are mixed with the ethyl acetate that its mass ratio is 75%, are 50~80 DEG C in temperature
Under the conditions of so that L- lactides or D- lactides is completely dissolved, room temperature is cooling and is placed in refrigerator and preserves overnight, miscellaneous having dissolved
The ethyl acetate of matter filters totally, purifies according to the method described above three times, finally L- lactides or D- lactides are vacuumized, extracted
All solvents obtain L- lactides or D- lactides after purification.
PDLA is dextrorotation polylactic acid in PDLA-PDMS-PDLA.
Lactide (DL-lactide) structural formula of the present invention is as follows：
The reaction equation of PLLA Macroscopic single crystals is as follows：
The synthesis of initiator：
First monomer addition：
Chain growth：
Chain tra nsfer：
Polymerization degree n ≈ 139~1112.
Polymerization degree n=polylactic acid number-average molecular weight/polylactic acid repetitive unit molecular weight (72),
MnThe n ≈ 1020 of=73499 PLLA.
The reaction equation of triblock copolymer PDLA-PDMS-PDLA synthesis is as follows：
M ≈ 135 (PDMS that number-average molecular weight is 10000), 1~972 (M of n ≈n=141350 PDLA-PDMS-PDLA
M ≈ 135, n ≈ 912).
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effect：
The preparation method of the polylactic acid base hydrophobic film of the present invention, is prepared with a kind of biodegradation type material polylactic acid
Polylactic acid base hydrophobic film makes l-lactic acid (PLLA) film and triblock polymer by the Stereocomplex effect of polylactic acid
PDLA-PDMS-PDLA films are had an effect, due to the low surface free energy in dimethyl silicone polymer (PDMS) silicon and
With block PDLA Stereocomplex effect occurs for PLLA polymer, generates surface microscopic topographic double action so that polylactic acid base is thin
There is film hydrophobic characteristic, the preparation method of polylactic acid base hydrophobic film of the invention to be simple and efficient, easy control of process conditions,
Uniform hydrophobic film can be prepared, there is larger actual application value.
The preparation method of the polylactic acid base hydrophobic film of the present invention makes PLLA film bases particular by Stereocomplex effect
Body and PDLA-PDMS-PDLA triblock polymer films react and prepare polylactic acid base hydrophobic film, PLLA films with
PDLA-PDMS-PDLA triblock copolymer films generate Stereocomplex effect and prepare polylactic acid base hydrophobic film.
Description of the drawings
Fig. 1 be the PLLA polymer solutions that molecular weight is 73499 and molecular weight be 141350, a concentration of 100mg/ml four
The polylactic acid base hydrophobic film that hydrogen furans triblock copolymer PDLA-PDMS-PDLA solution is formed at 100 DEG C (by annealing
Field emission scanning electron microscope figure 30min).
Fig. 2 be the PLLA polymer solutions that molecular weight is 73499 and molecular weight be 141350, a concentration of 100mg/ml four
The Flied emission for the polylactic acid base hydrophobic film (unannealed) that hydrogen furans triblock copolymer PDLA-PDMS-PDLA solution is formed is swept
Retouch electron microscope.
Fig. 3 is the X-ray diffractogram of polylactic acid base hydrophobic film, wherein a is that PLLA (molecular weight 73499) polymer is molten
For the film that liquid is formed by the X-ray diffractogram after the 30min that anneals at 100 DEG C, b is triblock copolymer PDLA-PDMS-PDLA
For the film that (molecular weight 141350) solution is formed by the X-ray diffractogram after the 30min that anneals at 100 DEG C, c is PLLA (molecules
The amount polylactic acid that 73499) polymer solution and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution are formed
For base hydrophobic film by the X-ray diffractogram after the 30min that anneals at 100 DEG C, sc represents Stereocomplex crystal, and hc represents homogeneous brilliant
Body.
Fig. 4 is the contact angle figure of polylactic acid base hydrophobic film, wherein a is PLLA (molecular weight 73499) thin polymer film
(unannealed), contact angle=85.5 °；B is PLLA (molecular weight 73499) thin polymer film (by the 30min that anneals at 100 DEG C),
Contact angle=58 °；C is triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) film (by annealing at 100 DEG C
30min), contact angle=95.49 °；D is PLLA (molecular weight 73499) polymer solutions and triblock copolymer PDLA-PDMS-
The polylactic acid base hydrophobic film (by the 30min that anneals at 100 DEG C) that PDLA (molecular weight 21036) solution is formed, contact angle=
126°；E is PLLA (molecular weight 73499) polymer solutions and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350)
The polylactic acid base hydrophobic film (by the 30min that anneals at 100 DEG C) that solution is formed, contact angle=138.25 °；F is PLLA (molecules
The amount polylactic acid that 73499) polymer solution and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution are formed
Base hydrophobic film (by the 30min that anneals at 180 DEG C), contact angle=125.75 °.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
The reagents and materials used in the present invention are commercially available or can be prepared by literature method.Unless otherwise stated, otherwise hundred
Divide than being calculated by weight with number.
Reagent and material used in the embodiment of the present invention is as follows：
L- lactides, medical grade, Corbion-Purac；D- lactides, medical grade, Corbion-Purac；Methyl lactate,
Analyze pure, Adamas Reagent Co, ltd；Stannous octoate analyzes pure, Adamas Reagent Co, ltd；PDMS(Mn=
10000), DMS-C23, GELEST, INC；PDMS(Mn=4500-5500), DMS-C21, GELEST, INC；PDMS(Mn=650-
850), DMS-C16, GELEST, INC；Toluene analyzes pure, Shanghai Wo Kai Bioisystech Co., Ltd；Anhydrous ether, analysis is pure,
The upper smooth Science and Technology Co., Ltd. of Haitai.
The preparation method of the polylactic acid base hydrophobic film of the present invention first synthesizes l-lactic acid (PLLA), the poly- breast of dextrorotation
The triblock copolymer (PDLA-PDMS-PDLA) of acid and dimethyl silicone polymer.PLLA is dissolved in organic solvent, is spin-coated on
PLLA thin polymer films, by certain annealing, the then spin coating three on PLLA thin polymer films again are prepared on glass slide
Polylactic acid base hydrophobic film is made by certain annealing in the organic solvent of block copolymer PDLA-PDMS-PDLA.
The preparation method of the polylactic acid base hydrophobic film of the present invention, using isomer PDLA and the tool of PLLA polymer
Triblock copolymer PDLA-PDMS-PDLA is formed by certain hydrophobic PDMS, then by triblock copolymer PDLA-PDMS-
The PDLA film preparations PLLA thin polymer film matrix surface relatively high in molecular weight.By containing low surface free energy in block
Silicon and the Stereocomplex of the PDLA in matrix PLLA polymer and block polymer to act on the surface microstructure to be formed total
Same-action prepares polylactic acid base hydrophobic film.
Initiator methyl lactate of the present invention is the solution of a concentration of 50mg/ml configured with dry toluene, octoate catalyst
Stannous is the solution of a concentration of 50mg/ml configured with dry toluene.
Embodiment 1
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and it is pungent that 10g L- lactides, 260ul methyl lactates, 1ml are added inside three-necked flask
Sour stannous, 30ml solvent toluenes take out to be placed in 130 DEG C of oil bath pan in glove box and react 3~5h.Addition is stored in ice
The 100ml anhydrous ethers of case are precipitated, and finally reaction solution are placed in cold-trap device to vacuumize and are extracted all solvents for 24 hours,
Obtain the PLLA polymer that molecular weight is 73499.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 200g D- lactides and its matter
Amount is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the D- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and 8.28g D- lactides, 0.3g PDMS (M are added inside three-necked flaskn=
10000), 500ul stannous octoates, 30ml solvent toluenes, taken out in glove box be placed on reaction 3 in 130 DEG C of oil bath pan~
5h, the 100ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the triblock copolymer PDLA-PDMS-PDLA that molecular weight is 141350 is obtained.
The configuration of PLLA polymer, triblock copolymer PDLA-PDMS-PDLA solution
Claim 1g PLLA polymer powders, the PLLA solution of a concentration of 100mg/ml is configured to dichloromethane dissolving.It weighs
1g triblock copolymer PDLA-PDMS-PDLA powder uses dichloromethane, tetrahydrofuran, dimethylformamide, mass ratio respectively
It is 1:4 tetrahydrofuran and the mixed solution of n-hexane, mass ratio 1:4 tetrahydrofuran and the mixed solution of dichloromethane,
It is each configured to the triblock copolymer PDLA-PDMS-PDLA solution of a concentration of 10mg/ml, 50mg/ml, 100mg/ml.
The preparation of PLLA thin polymer films
With the PLLA solution of above-mentioned a concentration of 100mg/ml, load is spin-coated on the spin speed of 6000r/min with spin coating instrument
It on slide, is preserved by room temperature, 100 DEG C of annealing 30min processing, obtains the PLLA thin polymer films that contact angle is 50 °~90 °.
The preparation of triblock copolymer PDLA-PDMS-PDLA films
With above-mentioned various concentration (10mg/ml, 50mg/ml, 100mg/ml), (dichloromethane, the tetrahydrochysene furan of different solvents
It mutters, dimethylformamide, mass ratio 1:4 tetrahydrofuran and the mixed solution of n-hexane, mass ratio 1:4 tetrahydrofuran
With the mixed solution of dichloromethane) triblock copolymer PDLA-PDMS-PDLA solution with spin coating instrument with the spin coating of 6000r/min
Speed is spin-coated on glass slide, is preserved by room temperature, 100 DEG C of annealing 30min processing, is obtained three that contact angle is 90 °~110 °
Block copolymer PDLA-PDMS-PDLA films.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution of above-mentioned a concentration of 100mg/ml, load is spin-coated on the spin speed of 6000r/min with spin coating instrument
On slide, then a concentration of 100mg/ml of spin coating, the triblock copolymer that solvent is tetrahydrofuran on PLLA thin polymer film matrixes
Object PDLA-PDMS-PDLA solution, room temperature preserves after 100 DEG C are annealed 30min.Obtained polylactic acid base hydrophobic film is done
Field emission scanning electron microscope (SEM), X-ray diffraction (XRD) and contact angle test.
Apparent Stereocomplex peak crystallization being can be seen that from XRD results to occur, contact angle test result is 110 °~
130°.Field emission scanning electron microscope is as shown in Figure 1, the PLLA polymer solutions and molecular weight that it is 73499 that Fig. 1, which is molecular weight, are
141350, the polylactic acid base that the tetrahydrofuran triblock copolymer PDLA-PDMS-PDLA solution of a concentration of 100mg/ml is formed is dredged
The field emission scanning electron microscope figure of water film (by the 30min that anneals at 100 DEG C).It can be seen from the figure that occur 0.5~
The layer stereo hole of 4.3um, XRD results, which show apparent Stereocomplex crystal, to be occurred, and Stereocomplex crystal structure is more equal
Gathering lactic acid crystals are more fine and close, and fine and close structure causes segment to shrink, so foring this layer stereo hole pattern.
X-ray diffraction is as shown in figure 3, Fig. 3 is the X-ray diffractogram of polylactic acid base hydrophobic film, wherein a is that PLLA (divides
Son measures the film of 73499) polymer solution formation by the X-ray diffractogram after the 30min that anneals at 100 DEG C, and b is total for three block
The film that polymers PDLA-PDMS-PDLA (molecular weight 141350) solution is formed is spread out by the X-ray after the 30min that anneals at 100 DEG C
Figure is penetrated, c is PLLA (molecular weight 73499) polymer solutions and triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350)
The polylactic acid base hydrophobic film that solution is formed represents Stereocomplex by the X-ray diffractogram after the 30min that anneals at 100 DEG C, sc
Crystal, hc represent homogeneous crystal.As can be seen from Figure, there is Stereocomplex in the polylactic acid base hydrophobic film after annealing
Crystal, it is (110), (300)/(030) that the diffraction maximum positioned at 2 θ=11.9 °, 20.7 ° and 23.9 °, which is respectively belonging to Miller indices,
(220) three-dimensional composite crystal crystallographic plane diffraction peak.
Test results are shown in figure 4 for contact angle, and Fig. 4 is the contact angle figure of polylactic acid base hydrophobic film, wherein a PLLA
(molecular weight 73499) thin polymer film (unannealed), contact angle=85.5 °；B is PLLA (molecular weight 73499) thin polymer film
(by the 30min that anneals at 100 DEG C), contact angle=58 °；C is triblock copolymer PDLA-PDMS-PDLA (molecular weight
141350) film (by the 30min that anneals at 100 DEG C), contact angle=95.49 °；D is that PLLA (molecular weight 73499) polymer is molten
The polylactic acid base hydrophobic film that liquid and triblock copolymer PDLA-PDMS-PDLA (molecular weight 21036) solution are formed (passes through 100
Anneal 30min at DEG C), contact angle=126 °；E is PLLA (molecular weight 73499) polymer solutions and triblock copolymer PDLA-
The polylactic acid base hydrophobic film (by the 30min that anneals at 100 DEG C) that PDMS-PDLA (molecular weight 141350) solution is formed, contact
Angle=138.25 °；F is PLLA (molecular weight 73499) polymer solutions and triblock copolymer PDLA-PDMS-PDLA (molecular weight
141350) the polylactic acid base hydrophobic film (by the 30min that anneals at 180 DEG C) that solution is formed, contact angle=125.75 °.It compares
It is carried respectively with unannealed pure PLLA thin polymer films, the contact angle of the polylactic acid base hydrophobic film after annealing after annealing
It is nearly 80 ° and 53 ° high, illustrate that adding the silicon containing low surface free energy by surface carries out chemical modification and due to Stereocomplex
The rough surface pattern collective effect of generation, can prepare polylactic acid base hydrophobic film.
Embodiment 2
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and it is pungent that 10g L- lactides, 260ul methyl lactates, 1ml are added inside three-necked flask
Sour stannous, 30ml solvent toluenes take out to be placed in 130 DEG C of oil bath pan in glove box and react 3~5h.Addition is stored in ice
The 100ml anhydrous ethers of case are precipitated, and finally reaction solution are placed in cold-trap device to vacuumize and are extracted all solvents for 24 hours,
Obtain the PLLA polymer that molecular weight is 73499.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 200g D- lactides and its matter
Amount is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the D- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and 8.28g D- lactides, 0.3g PDMS (M are added inside three-necked flaskn=
10000), 500ul stannous octoates, 30ml solvent toluenes, taken out in glove box be placed on reaction 3 in 130 DEG C of oil bath pan~
5h, the 100ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the triblock copolymer PDLA-PDMS-PDLA that molecular weight is 141350 is obtained.
The configuration of PLLA polymer, triblock copolymer PDLA-PDMS-PDLA solution
Claim 1g PLLA polymer powders, the PLLA solution of a concentration of 100mg/ml is configured to dichloromethane dissolving.It weighs
1g triblock copolymer PDLA-PDMS-PDLA powder uses dichloromethane, tetrahydrofuran, dimethylformamide, mass ratio respectively
It is 1:4 tetrahydrofuran and the mixed solution of n-hexane, mass ratio 1:4 tetrahydrofuran and the mixed solution of dichloromethane,
It is each configured to the triblock copolymer PDLA-PDMS-PDLA solution of a concentration of 10mg/ml, 50mg/ml, 100mg/ml.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution of above-mentioned a concentration of 100mg/ml, load is spin-coated on the spin speed of 6000r/min with spin coating instrument
On slide, by 100 DEG C of annealing 30min, then a concentration of 100mg/ml of spin coating, solvent four on PLLA thin polymer film matrixes
The triblock copolymer PDLA-PDMS-PDLA solution of hydrogen furans, room temperature preserves after 100 DEG C are annealed 30min.What is obtained
Polylactic acid base hydrophobic film does field emission scanning electron microscope (SEM), X-ray diffraction (XRD) and contact angle test.It can from XRD results
To find out, there is apparent Stereocomplex peak crystallization to occur, contact angle test result is 110 °~140 °.
Embodiment 3
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and L- lactides 5g, methyl lactate 130ul (lactic acid first are added inside three-necked flask
Ester is the solution of a concentration of 50mg/ml configured with dry toluene), (stannous octoate is matched with dry toluene to stannous octoate 500ul
The solution of a concentration of 50mg/ml set), solvent toluene 15ml, take out to be placed in 130 DEG C of oil bath pan in glove box and react
5h, the 60ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the PLLA polymer that molecular weight is 73499 is obtained.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 20g D- lactides and its quality
Than the ethyl acetate mixing for 75%, it is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator mistake
Night filters the ethyl acetate for having dissolved impurity totally, purifies three times, the D- lactides of purifying are put according to the method described above finally
It is vacuumized in cold-trap device and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and D- lactide 8.28g, PDMS (M are added inside three-necked flaskn=10000)
0.3g, stannous octoate 828ul (stannous octoate is the solution of a concentration of 50mg/ml configured with dry toluene), solvent toluene
30ml takes out to be placed in 130 DEG C of oil bath pan in glove box and reacts 5h, the 100ml anhydrous ethers for being stored in refrigerator are added
It is precipitated, finally reaction solution is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours, obtaining molecular weight is
141350 triblock copolymer PDLA-PDMS-PDLA.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution (solvent is dichloromethane) of above-mentioned a concentration of 100mg/ml, with spin coating instrument with 6000r/min's
Spin speed is spin-coated on glass slide, then on PLLA thin polymer film matrixes spin coating tetrahydrofuran as solvent, a concentration of
The triblock copolymer PDLA-PDMS-PDLA solution of 100mg/ml, room temperature preserves after 100 DEG C are annealed 30min.Obtaining
Polylactic acid base hydrophobic film do field emission scanning electron microscope (SEM), X-ray diffraction (XRD) and contact angle test, after annealing
Polylactic acid base hydrophobic film mostly many solids obviously than unannealed polylactic acid base hydrophobic film can be seen that by SEM
Hole, in conjunction with XRD it is found that the appearance of Stereocomplex can have a huge impact film surface appearance.PLLA polymer thins
The contact angle of film is 85.5 °, is reduced to 58 ° after the 30min that anneals at 100 DEG C, triblock copolymer PDLA-PDMS-PDLA
The contact angle of film (by the 30min that anneals at 100 DEG C) is 95.49 °, and final polylactic acid base hydrophobic film is (by 100 DEG C
Anneal 30min) contact angle=138.25 °.Compared to the PLLA thin polymer films after annealing, the polylactic acid base after annealing is hydrophobic
Film contacts angle improves nearly 80 °.
Embodiment 4
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and L- lactides 5g, methyl lactate 130ul (lactic acid first are added inside three-necked flask
Ester is the solution of a concentration of 50mg/ml configured with dry toluene), (stannous octoate is matched with dry toluene to stannous octoate 500ul
The solution of a concentration of 50mg/ml set), solvent toluene 15ml, take out to be placed in 130 DEG C of oil bath pan in glove box and react
5h, the 60ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the PLLA polymer that molecular weight is 73499 is obtained.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 20g D- lactides and its quality
Than the ethyl acetate mixing for 75%, it is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator mistake
Night filters the ethyl acetate for having dissolved impurity totally, purifies three times, the D- lactides of purifying are put according to the method described above finally
It is vacuumized in cold-trap device and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and D- lactide 5g, PDMS (M are added inside three-necked flaskn=10000) 2.5g,
Stannous octoate 500ul (stannous octoate is the solution of a concentration of 50mg/ml configured with dry toluene), solvent toluene 20ml, from
It taking out to be placed in 130 DEG C of oil bath pan in glove box and reacts 4h, the 60ml anhydrous ethers that addition is stored in refrigerator are precipitated,
Finally reaction solution is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours, obtains the three block that molecular weight is 21036
Copolymer p DLA-PDMS-PDLA.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution (solvent is dichloromethane) of above-mentioned a concentration of 100mg/ml, with spin coating instrument with 6000r/min's
Spin speed is spin-coated on glass slide, then on PLLA thin polymer film matrixes spin coating tetrahydrofuran as solvent, a concentration of
Triblock copolymer PDLA-PDMS-PDLA (molecular weight 21036) solution of 100mg/ml, after 100 DEG C are annealed 30min
Room temperature preserves.Contact angle=125.99 ° of final polylactic acid base hydrophobic film (by the 30min that anneals at 100 DEG C), the implementation
Polylactic acid base hydrophobic film prepared by example is weaker compared with the hydrophobicity of polylactic acid base hydrophobic film prepared by embodiment 3, is
Because when PLLA and PDLA chain lengths are close, it is easier to form Stereocomplex crystal.The polymerization of PLLA and PDLA in embodiment 3
Degree is respectively 1020 and 912；The degree of polymerization of PLLA and PDLA is respectively 1020 and 77 in the present embodiment.
Comparative example 1
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and it is pungent that 10g L- lactides, 260ul methyl lactates, 1ml are added inside three-necked flask
Sour stannous, 30ml solvent toluenes take out to be placed in 130 DEG C of oil bath pan in glove box and react 3~5h.Addition is stored in ice
The 100ml anhydrous ethers of case are precipitated, and finally reaction solution are placed in cold-trap device to vacuumize and are extracted all solvents for 24 hours,
Obtain the PLLA polymer that molecular weight is 73499.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 200g D- lactides and its matter
Amount is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the D- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and 8.28g D- lactides, 0.3g PDMS (M are added inside three-necked flaskn=
10000), 500ul stannous octoates, 30ml solvent toluenes, taken out in glove box be placed on reaction 3 in 130 DEG C of oil bath pan~
5h, the 100ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the triblock copolymer PDLA-PDMS-PDLA that molecular weight is 141350 is obtained.
The configuration of PLLA polymer, triblock copolymer PDLA-PDMS-PDLA solution
Claim 1g PLLA polymer powders, the PLLA solution of a concentration of 100mg/ml is configured to dichloromethane dissolving.It weighs
1g triblock copolymer PDLA-PDMS-PDLA powder uses dichloromethane, tetrahydrofuran, dimethylformamide, mass ratio respectively
It is 1:4 tetrahydrofuran and the mixed solution of n-hexane, mass ratio 1:4 tetrahydrofuran and the mixed solution of dichloromethane,
It is each configured to the triblock copolymer PDLA-PDMS-PDLA solution of a concentration of 10mg/ml, 50mg/ml, 100mg/ml.
The preparation of PLLA thin polymer films
With the PLLA solution of above-mentioned a concentration of 100mg/ml, load is spin-coated on the spin speed of 6000r/min with spin coating instrument
It on slide, is preserved by room temperature, 100 DEG C of annealing 30min processing, obtains the PLLA thin polymer films that contact angle is 50 °~90 °.
The preparation of triblock copolymer PDLA-PDMS-PDLA films
With above-mentioned various concentration (10mg/ml, 50mg/ml, 100mg/ml), (dichloromethane, the tetrahydrochysene furan of different solvents
It mutters, dimethylformamide, mass ratio 1:4 tetrahydrofuran and the mixed solution of n-hexane, mass ratio 1:4 tetrahydrofuran
With the mixed solution of dichloromethane) triblock copolymer PDLA-PDMS-PDLA solution with spin coating instrument with the spin coating of 6000r/min
Speed is spin-coated on glass slide, is preserved by room temperature, 100 DEG C of annealing 30min processing, is obtained three that contact angle is 90 °~110 °
Block copolymer PDLA-PDMS-PDLA films.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution of above-mentioned a concentration of 100mg/ml, load is spin-coated on the spin speed of 6000r/min with spin coating instrument
On slide, then a concentration of 100mg/ml of spin coating on PLLA thin polymer film matrixes), the triblock copolymer that solvent is tetrahydrofuran
Object PDLA-PDMS-PDLA solution, preserves by room temperature, and obtained polylactic acid base hydrophobic film is done field emission scanning electron microscope
(SEM), X-ray diffraction (XRD) and contact angle test.
Faint Stereocomplex peak crystallization being can be seen that from XRD results to occur, contact angle test result is 100 °~
115°.Field emission scanning electron microscope is as shown in Fig. 2, the PLLA polymer solutions and molecular weight that it is 73499 that Fig. 2, which is molecular weight, are
141350, the polylactic acid base that the tetrahydrofuran triblock copolymer PDLA-PDMS-PDLA solution of a concentration of 100mg/ml is formed is dredged
The field emission scanning electron microscope figure of water film (unannealed).It can be seen from the figure that there is the hole of 1.5um~5.5um, it is this
Hole is formed since solvent volatilizees.Without other special microscopic appearances in figure, illustrate compared to pure PLLA thin polymer films,
The hydrophobicity raising of this unannealed polylactic acid base hydrophobic film is due to containing in triblock copolymer PDLA-PDMS-PDLA
There is the silicon of low surface free energy.
Comparative example 2
The synthesis of PLLA polymer
The purifying of L- lactides：Raw material L- lactides ethyl acetate is purified 3 times, 200g L- lactides and its matter
Amount is completely dissolved L- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator than being mixed for 75% ethyl acetate
Overnight, the ethyl acetate for having dissolved impurity is filtered totally, is purified according to the method described above three times, finally the L- lactides of purifying
It is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and L- lactides 5g, methyl lactate 130ul (lactic acid first are added inside three-necked flask
Ester is the solution of a concentration of 50mg/ml configured with dry toluene), (stannous octoate is matched with dry toluene to stannous octoate 500ul
The solution of a concentration of 50mg/ml set), solvent toluene 15ml, take out to be placed in 130 DEG C of oil bath pan in glove box and react
5h, the 60ml anhydrous ethers that addition is stored in refrigerator are precipitated, finally reaction solution are placed in cold-trap device and is vacuumized for 24 hours,
All solvents are extracted, the PLLA polymer that molecular weight is 73499 is obtained.
The synthesis of triblock copolymer PDLA-PDMS-PDLA
The purifying of D- lactides：Raw material D- lactides ethyl acetate is purified 3 times, 20g D- lactides and its quality
Than the ethyl acetate mixing for 75%, it is completely dissolved D- lactides under 60 DEG C of water-bath, room temperature is cooling and places refrigerator mistake
Night filters the ethyl acetate for having dissolved impurity totally, purifies three times, the D- lactides of purifying are put according to the method described above finally
It is vacuumized in cold-trap device and extracts all solvents for 24 hours.
Weighing is carried out in glove box, and D- lactide 8.28g, PDMS (M are added inside three-necked flaskn=10000)
0.3g, stannous octoate 828ul (stannous octoate is the solution of a concentration of 50mg/ml configured with dry toluene), solvent toluene
30ml takes out to be placed in 130 DEG C of oil bath pan in glove box and reacts 5h, the 100ml anhydrous ethers for being stored in refrigerator are added
It is precipitated, finally reaction solution is placed in cold-trap device to vacuumize and extracts all solvents for 24 hours, obtaining molecular weight is
141350 triblock copolymer PDLA-PDMS-PDLA.
The preparation of polylactic acid base hydrophobic film
By the PLLA solution (solvent is dichloromethane) of above-mentioned a concentration of 100mg/ml, molecular weight 73499, with spin coating instrument
It is spin-coated on glass slide with the spin speed of 6000r/min, then the spin coating tetrahydrofuran conduct on PLLA thin polymer film matrixes
Triblock copolymer PDLA-PDMS-PDLA (molecular weight 141350) solution of solvent, a concentration of 100mg/ml, by 180 DEG C
Room temperature preserves after annealing 30min.The contact angle of final polylactic acid base hydrophobic film (by the 30min that anneals at 180 DEG C)=
125.75°.Polylactic acid base hydrophobic film manufactured in the present embodiment is hydrophobic with the polylactic acid base hydrophobic film that is prepared in embodiment 3
Property compared to poor, be because 180 DEG C be polylactic acid melting temperature, the excessively high microcosmic shape for destroying polylactic acid primary surface of temperature
Looks result in its hydrophobic reduction.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method of polylactic acid base hydrophobic film, it is characterised in that：Include the following steps：
L-lactic acid thin polymer film is made in l-lactic acid polymer solution, by triblock copolymer PDLA-PDMS-
PDLA solution is spun on above-mentioned l-lactic acid thin polymer film matrix, by annealing, obtains the polylactic acid base
Hydrophobic film.
2. the preparation method of polylactic acid base hydrophobic film according to claim 1, it is characterised in that：The polylactic acid base is dredged
The preparation method of water film further includes：L-lactic acid thin polymer film is by annealing.
3. the preparation method of polylactic acid base hydrophobic film according to claim 1 or 2, it is characterised in that：It is described left-handed poly-
Lactic acid polymer solution is that l-lactic acid is dissolved in organic solvent, a concentration of 1~200mg/ml, preferably 100mg/ml；
The triblock copolymer PDLA-PDMS-PDLA solution be triblock copolymer PDLA-PDMS-PDLA is dissolved in it is organic
In solvent, a concentration of 1~200mg/ml, preferably 100mg/ml；
Preferably, the organic solvent is the mixed of dichloromethane, tetrahydrofuran, dimethylformamide, tetrahydrofuran and n-hexane
Close at least one of the mixed solution of solution, tetrahydrofuran and dichloromethane, preferably dichloromethane, tetrahydrofuran.
4. the preparation method of polylactic acid base hydrophobic film according to claim 1 or 2, it is characterised in that：At the annealing
Reason is the 10~60min that anneals under conditions of temperature is 80~180 DEG C, and preferred temperature is 100 DEG C, time 30min.
5. the preparation method of polylactic acid base hydrophobic film according to claim 1 or 2, it is characterised in that：It is described left-handed poly-
The number-average molecular weight of lactic acid polymer is 10000~80000, preferably 73499；
The number-average molecular weight of the triblock copolymer PDLA-PDMS-PDLA is 10000~170000, preferably 141350.
6. the preparation method of polylactic acid base hydrophobic film according to claim 1 or 2, it is characterised in that：It is described left-handed poly-
The preparation method of lactic acid polymer includes the following steps：
In anhydrous, anaerobic, dustless environment, L- lactides, initiator, catalysts and solvents after purification are weighed, are in temperature
Under conditions of 110~150 DEG C reaction 1~for 24 hours, cold ether is added and is precipitated, the l-lactic acid is obtained after vacuumizing
Polymer.
7. the preparation method of polylactic acid base hydrophobic film according to claim 6, it is characterised in that：The initiator and L-
The mass ratio of lactide is (1~2):1000, preferably 1.3:1000；
The mass ratio of the catalyst and L- lactides is (1~10):1000, preferably 5:1000；
The L- lactides are dissolved in a concentration of 0.25~0.5g/ml of solvent, preferably 0.33g/ml；
The initiator is methyl lactate, lactic acid, laruyl alcohol, preferably methyl lactate；
The catalyst is stannous octoate, zinc oxide；
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane, hexamethylene.
8. the preparation method of polylactic acid base hydrophobic film according to claim 1 or 2, it is characterised in that：The three block
The preparation method of copolymer p DLA-PDMS-PDLA includes the following steps：
In anhydrous, anaerobic, dustless environment, D- lactides, initiator, catalysts and solvents after purification are weighed, are in temperature
Under conditions of 110~150 DEG C reaction 1~for 24 hours, cold ether is added and is precipitated, the triblock copolymer is obtained after vacuumizing
Object PDLA-PDMS-PDLA.
9. the preparation method of polylactic acid base hydrophobic film according to claim 8, it is characterised in that：The initiator and D-
The mass ratio of lactide is (0.01~0.8):1, preferably (0.03~0.5):1；
The mass ratio of the catalyst and D- lactides is (1~10):1000, preferably (3~5):1000；
The D- lactides are dissolved in a concentration of 0.1~0.5g/ml of solvent, preferably 0.2~0.3g/ml；
The initiator is Mn=10000,4500~5500,600~850 dimethyl silicone polymer, preferably Mn=10000
Dimethyl silicone polymer；
The catalyst is stannous octoate, zinc oxide；
The solvent is at least one of toluene, tetrahydrofuran, dichloromethane, hexamethylene.
10. the preparation method of the polylactic acid base hydrophobic film according to claim 6 or 8, it is characterised in that：The L- third is handed over
By purifying, purifying includes the following steps for ester or D- lactides：
L- lactides or D- lactides are mixed with the ethyl acetate that its mass ratio is 75%, the condition for being 50~80 DEG C in temperature
Under so that L- lactides or D- lactides is completely dissolved, room temperature is cooling and is placed in refrigerator and preserves overnight, having dissolved impurity
Ethyl acetate filters totally, purifies three times, L- lactides or D- lactides are vacuumized according to the method described above finally, extract all
Solvent, obtain L- lactides or D- lactides after purification.
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| CN111961348B (en) * | 2020-08-27 | 2022-03-15 | 内蒙古农业大学 | Polylactic acid copolymer film with siloxane side chain, preparation method thereof and application thereof in fruit and vegetable fresh keeping |
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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 |
| CN114642970A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Nano fiber membrane attached with POSS-PMMA-b-PDMS super-hydrophobic compound and preparation method |
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| CN113444348A (en) * | 2021-06-01 | 2021-09-28 | 长江师范学院 | Polylactic acid stereocomplex, preparation method and application |
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