CN102516507A - Preparation method for polylactic acid-ferroferric oxide nanometer composite materials - Google Patents
Preparation method for polylactic acid-ferroferric oxide nanometer composite materials Download PDFInfo
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- CN102516507A CN102516507A CN2011103835269A CN201110383526A CN102516507A CN 102516507 A CN102516507 A CN 102516507A CN 2011103835269 A CN2011103835269 A CN 2011103835269A CN 201110383526 A CN201110383526 A CN 201110383526A CN 102516507 A CN102516507 A CN 102516507A
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Abstract
The invention provides a preparation method for polylactic acid-ferroferric oxide nanometer composite materials. In a high pressure reactor, modified nanometer ferroferric oxide is obtained firstly, lactide, a catalyst, the modified nanometer ferroferric oxide and solvent are added proportionally, reaction temperature and reaction time are controlled to enable mixed solution to be reacted in a high-temperature airtight system, monomer, the catalyst, nanometer particles and the solvent are contacted fully and cannot volatilize so as to enable reaction to be completely, and reaction solution is precipitated, filtered and dried to obtain the polylactic acid-ferroferric oxide nanometer composite materials. The obtained polylactic acid-ferroferric oxide nanometer composite materials have good dispersity and superparamagetism, and the preparation method is temperate in reaction conditions and simple and has good large-scale production prospect.
Description
Technical field
The present invention relates to technical field of composite materials, relate in particular to a kind of solvent thermal synthesis method that in autoclave, adopts and prepare the method for POLYACTIC ACID-ferriferrous oxide nano matrix material.
Background technology
PLA extracts starch from starch-containing farm crop such as corn, obtain lactic acid through fermentation, and lactic acid makes through one of polycondensation, azeotropic dehydrogenative condensation or three kinds of approach of rac-Lactide ring-opening polymerization again, and under discarded composting conditions, PLA can finally directly be degraded to CO
2And H
2O; It has advantages such as excellent biological compatibility, bioresorbable, degradation property, nontoxic nonirritant, sustainability; Thereby receive concern widely, especially have comparatively widely and use at biomedical sectors such as operating suture, fracture internal fixing, controlled drug delivery system and tissue engineering bracket materials.And in order to give the POLYACTIC ACID functionalization and to enlarge its range of application, the hybrid material of POLYACTIC ACID and inorganic nanoparticles also more and more receives and paying close attention to widely, like POLYACTIC ACID/TiO
2Matrix material (Zhuan Wei; Zhang Jianhua etc., matrix material journal, 25 (3): 8-11; Full long battle array; Zhang Chunmei etc., polymer material science and engineering, 26 (12): 99-102), the compound (CN200610053891.2 of POLYACTIC ACID and Win 40350; CN200710157568.4 etc.; Jiang Xiaoting; Wang Qian etc., chemical research and application, 23 (6): 755-760), POLYACTIC ACID and montmorillonite composite material (CN200610010279.7; CN200710171659.3; CN200510030494.9 etc.); POLYACTIC ACID and silicon dioxide composite material (Zhou Haiou; Shi Tiejun etc., polymer material science and engineering, 22 (2): 220-226), POLYACTIC ACID/CdSe/ZnS matrix material (Lee, YK; Hong, SM; Kim, JS, et al., MACROMOLECULAR RESEARCH, 15 (4): 330-336), POLYACTIC ACID and ferriferrous oxide composite material (Alexandrina Nan; Rodica Turcu, et al., Journal of Physics:ConferenceSeries, 182:1-4; Hong Zhao; Katayoun Saatchi; Urs O.
, Journal of Magnetismand Magnetic Materials, 321:1356-1363 etc.).POLYACTIC ACID-ferriferrous oxide composite material has certain application prospect at biology or medical field, such as: biomass cells mark with separate, targeted drug, medicament transport, nucleic acid concentrate, biochemical investigation etc., but most of POLYACTIC ACIDs and the compound of Z 250 all are through letex polymerization (Katharina Landfester; Angewandte Chemie; 48:4488-4507 etc.), self-assembly, methods such as anionoid polymerization obtain; These reaction process more complicated, and wayward.
Summary of the invention
The objective of the invention is to overcome existing preparation POLYACTIC ACID-ferriferrous oxide nano composite process reaction process more complicated; And it is wayward etc. not enough; A kind of preparation method of new POLYACTIC ACID-ferriferrous oxide nano matrix material is provided, and the nano composite material of preparation has good functional characteristics such as superparamagnetism, and method is simple; Reaction conditions is gentle, is convenient to scale operation.
For realizing this purpose; In technical scheme of the present invention; Preparing method-solvent thermal the synthesis method that adopts; Its reaction mechanism is different from the method that emulsion method in the past prepares poly lactic acid nano composite material, is the method that the polymerization of the modification of nano ferriferrous oxide and POLYACTIC ACID is all carried out in autoclave.In autoclave; Put into nano ferriferrous oxide, properties-correcting agent and solvent by a certain percentage; Control reaction temperature and time are reacted mixing solutions in the high temperature enclosed system, then with the nano ferriferrous oxide after the modification wash, centrifugal and dry.Then in autoclave; Put into rac-Lactide, catalyzer, improved ferroferric oxide nanometer and solvent by a certain percentage; Monomer, catalyzer, ferriferrous oxide nano and solvent are fully contacted, and can not volatilize, react completely thereby make; Then that the reaction soln sedimentation and filtration is dry, promptly obtain POLYACTIC ACID-ferriferrous oxide nano matrix material.
The objective of the invention is to realize through following technical scheme:
The present invention relates to the preparation method of a kind of POLYACTIC ACID-ferriferrous oxide nano matrix material, comprise the steps:
The first step, the preparation of modified Nano Z 250:
A, in weight part, in autoclave, add 20～80 parts of nano ferriferrous oxides, 1～25 part of coupling agent, 0～10 part of coupling agent hydrolytic accelerating agent and 15～50 parts of solvents 1, said solvent 1 is one or more in THF, the alcohol organic solvent;
B, before reaction, feed nitrogen in the autoclave to remove oxygen, sealing places reaction constant temperature under, takes out reactant afterwards, cools off;
C, open autoclave, product carries out after with said solvent 1 washing centrifugal, and drying promptly obtains the nano ferriferrous oxide after the modification.
Second step, POLYACTIC ACID-ferriferrous oxide nano Composite Preparation:
A, in weight part; In autoclave, add nano ferriferrous oxide and 25～60 parts of solvents 2 after 25～70 parts rac-Lactide, 0.05～1 part catalyzer, 0～5 part of stablizer, 1～20 part of the first step modification, said solvent 2 is one or more in THF, ketone, halogenated hydrocarbon, the aromatic hydrocarbons organic solvent;
B, before reaction, feed nitrogen in the autoclave to remove oxygen, sealing places reaction constant temperature under, takes out reactant afterwards, cools off;
C, open autoclave, pour reaction soln in ethanol sedimentation and filtration, and with the washing with alcohol deposition until washing out unreacted reactant fully, suction filtration then, drying promptly obtains POLYACTIC ACID-ferriferrous oxide nano matrix material.
Preferably, the particle size of nano ferriferrous oxide described in the first step step a is 10～200nm.
Preferably, coupling agent described in the first step step a is silane coupling agent, titante coupling agent or both mixtures.
Preferably, coupling agent hydrolytic accelerating agent described in the first step step a is acetic acid, hydrochloric acid, organotin or combination in twos.
Preferably, alcohol organic solvent described in the first step step a is ethanol, methyl alcohol and Virahol.
Preferably, place described in the first step step b to react under the constant temperature to be specially, reaction kettle is placed in 80～180 ℃ of thermostat containers, reacted 3～8 hours.
Preferably, drying was specially described in the first step step c: with the centrifugal powder that obtains in 60～90 ℃ of vacuum drying ovens dry 12～36 hours.
Preferably, catalyzer described in the second rapid step by step a is one or more the mixture in tetravalence alkyl alkoxy tin, tetravalence tin aryl SnAr2, stannous salt, magnesium complex, aluminum alkyls, aluminum alkoxide, the zinc complex.
Preferably, stablizer is DBPC 2,6 ditertiary butyl p cresol, four [β-(3 described in the second rapid step by step a; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, two (2,2,6; 6-tetramethyl--4-sebate, Tyox B, β-(3; The 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, N '-two-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group) hexanediamine, 4; The mixture of one or more in 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), two (3,5-di-t-butyl-4 hydroxybenzyl monoethyl phosphate) nickel.
Preferably; Organic solvent of ketone is acetone, butanone, pimelinketone, toluene pimelinketone and mibk described in the second rapid step by step a; Said halogenated hydrocarbon organic solvent is 1; 2-ethylene dichloride, 1,2-methylene dichloride, chloroform and tetracol phenixin, said aromatic hydrocarbons organic solvent is toluene, benzene and YLENE.
Preferably, placing described in the second rapid step by step b reacted constant temperature under and is specially, and reaction kettle is placed in 120～200 ℃ of thermostat containers, reacts 5～12 hours.
Preferably, drying is specially described in the second rapid step by step c: the powder that suction filtration is obtained in 60～90 ℃ of vacuum drying ovens dry 12～36 hours.
Compared with prior art, the beneficial effect that has of the present invention is: the POLYACTIC ACID that the present invention prepares-ferriferrous oxide nano composite powder has good dispersiveness and superparamagnetism; The amount of solvent for use is less relatively in the reaction process of the present invention; Reaction conditions is gentle; The preparation method is simple; Possess good large-scale production prospect, and certain application prospect arranged at biology or medical field, such as: biomass cells mark with separate, targeted drug, medicament transport, nucleic acid concentrates and biochemical investigation etc.
Description of drawings
The TEM transmission electron microscope photo of the POLYACTIC ACID that Fig. 1 makes for embodiment 1-ferriferrous oxide nano matrix material;
The magnetization curve of the POLYACTIC ACID that Fig. 2 makes for embodiment 3-ferriferrous oxide nano matrix material.
Embodiment
Below technical scheme of the present invention is described in detail through accompanying drawing and concrete embodiment.Following examples are to further specify of the present invention, rather than limit scope of the present invention.
Embodiment 1
The first step is put into 5g nano ferriferrous oxide (particle size is 20nm), 5g γ-(methacryloxypropyl) propyl trimethoxy silicane, 40g ethanol in autoclave, feed nitrogen in the autoclave to remove oxygen; The autoclave lid tightened put into 160 ℃ baking oven; Placed 6 hours, and took out naturally cooling then, with washing with alcohol, centrifugal; With the centrifugal powder that obtains in 60 ℃ of vacuum drying ovens dry 36 hours, promptly obtain the nano ferriferrous oxide of modification.Second step, in autoclave, put into nano ferriferrous oxide, the 7.5g toluene of 20g rac-Lactide, 0.06g tin protochloride, 1g modification, feed nitrogen 5 minutes in the autoclave to remove oxygen; The autoclave lid tightened put into 200 ℃ baking oven, placed 5 hours, take out then and use water cooling; Open autoclave, pour reaction soln in ethanol post precipitation filtration, and precipitate 5 times with washing with alcohol; Suction filtration then; The powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 24 hours promptly obtains POLYACTIC ACID-ferriferrous oxide nano matrix material, and is as shown in Figure 1.Fig. 1 is the Electronic Speculum figure of POLYACTIC ACID-ferriferrous oxide nano matrix material of making under this condition, and as can be seen from the figure nano composite material has good dispersiveness, and size is about 30nm, and showing has POLYACTIC ACID to be coated on the Z 250 surface.
Embodiment 2
The first step is put into 8g nano ferriferrous oxide (particle size is 50nm), 0.5g vinyltrimethoxy silane, 1g aqueous acetic acid, 15g methyl alcohol in autoclave, feed nitrogen 5 minutes in the autoclave to remove oxygen; The autoclave lid tightened put into 180 ℃ baking oven; Placed 3 hours, and took out naturally cooling then, with methanol wash, centrifugal; With the centrifugal powder that obtains in 70 ℃ of vacuum drying ovens dry 28 hours, promptly obtain the nano ferriferrous oxide of modification.In second step, in autoclave, put into 10g rac-Lactide, 0.02g tetraphenylporphyrin aluminium alkoxy compound, 0.48g four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the nano ferriferrous oxide of 8g modification, 21.5g acetone; Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 180 ℃ baking oven, placed 8 hours; Take out then and use water cooling, open autoclave, pour reaction soln in ethanol post precipitation filtration; And with washing with alcohol deposition 5 times; Suction filtration then, the powder that suction filtration is obtained in 90 ℃ of vacuum drying ovens dry 12 hours promptly obtain POLYACTIC ACID-ferriferrous oxide nano matrix material.
Embodiment 3
The first step; In autoclave, put into 22g nano ferriferrous oxide (particle size is 150nm), 3g γ-glycidyl ether oxygen propyl trimethoxy silicane, 5g tetrabutyl titanate, 4g aqueous hydrochloric acid, 6g Virahol; Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 80 ℃ baking oven, placed 8 hours; Take out naturally cooling then; With washing with alcohol, centrifugal,, promptly obtain the nano ferriferrous oxide of modification with the centrifugal powder that obtains in 80 ℃ of vacuum drying ovens dry 20 hours.In second step, in autoclave, put into 13.2g rac-Lactide, 0.4g tin aryl SnAr2 (tetravalence), 1g two (2,2; 6,6-tetramethyl--4-sebate, 1g three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, the nano ferriferrous oxide of 0.4g modification, 24g pimelinketone feed nitrogen 5 minutes to remove oxygen in the autoclave; The autoclave lid tightened put into 120 ℃ baking oven, placed 12 hours, take out then and use water cooling; Open autoclave; Pour reaction soln in ethanol post precipitation filtration, and precipitate 5 times, then suction filtration with washing with alcohol; The powder that suction filtration is obtained in 60 ℃ of vacuum drying ovens dry 36 hours promptly obtains POLYACTIC ACID-ferriferrous oxide nano matrix material.The POLYACTIC ACID that obtains-ferriferrous oxide nano matrix material has good diamagnetism, and is as shown in Figure 2.Fig. 2 is the magnetzation curve of nano composite material, and as can be seen from the figure, magnetic compound particles has superparamagnetism, and along with weakening of magnetic field, the specific magnetising moment of magnet is reduced to 0 by stationary value, when T=0, does not have coercive force and remanent magnetism.
Embodiment 4
The first step; In autoclave, put into 28g nano ferriferrous oxide (particle size is 10nm), 0.4g organotin, 1.6g (acetylacetone based) metatitanic acid diisopropyl ester, 10g Virahol and alcoholic acid mixing solutions (ratio is 1: 1); Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 120 ℃ baking oven, placed 6 hours; Take out naturally cooling then; With washing with alcohol, centrifugal,, promptly obtain the nano ferriferrous oxide of modification with the centrifugal powder that obtains in 90 ℃ of vacuum drying ovens dry 12 hours.Second step, in autoclave, put into nano ferriferrous oxide, the 8g chloroform of 12g rac-Lactide, 0.1g tin protochloride, 0.1g zinc complex, 0.1g Tyox B, 4g modification, feed nitrogen 5 minutes in the autoclave to remove oxygen; The autoclave lid tightened put into 150 ℃ baking oven, placed 10 hours, take out then and use water cooling; Open autoclave; Pour reaction soln in ethanol post precipitation filtration, and precipitate 5 times, then suction filtration with washing with alcohol; The powder that suction filtration is obtained in 70 ℃ of vacuum drying ovens dry 18 hours promptly obtains POLYACTIC ACID-ferriferrous oxide nano matrix material.
Embodiment 5
The first step; In autoclave, put into 20g nano ferriferrous oxide (particle size is 200nm), 3g γ-An Bingjisanyiyangjiguiwan, 1g hydrochloric acid soln, 0.1g organotin, 15.9g THF; Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 100 ℃ baking oven, placed 6 hours; Take out naturally cooling then; With THF washing, centrifugal,, promptly obtain the nano ferriferrous oxide of modification with the centrifugal powder that obtains in 65 ℃ of vacuum drying ovens dry 32 hours.Second step, in autoclave, put into 16g rac-Lactide, 0.1g aluminum alkyls, 0.6g N, N '-two-(3-(3; The 5-di-tert-butyl-hydroxy phenyl) mixing solutions of the nano ferriferrous oxide of hexanediamine, 1.3g modification, 12g acetone and toluene (ratio is 1: 2) propionyl group) feeds nitrogen 5 minutes to remove oxygen in the autoclave, the autoclave lid is tightened put into 130 ℃ baking oven; Placed 10 hours; Take out then and use water cooling, open autoclave, pour reaction soln in ethanol post precipitation filtration; And with washing with alcohol deposition 5 times; Suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 26 hours promptly obtain POLYACTIC ACID-ferriferrous oxide nano matrix material.
Embodiment 6
The first step; In autoclave, put into mixture (ratio is 1: 9), 10.6g THF and the 10g ethanol of 18g nano ferriferrous oxide (particle size is 100nm), 0.4g γ-mercapto propyl-triethylsilicane alkane, 1g organotin and acetic acid; Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 140 ℃ baking oven, placed 5 hours; Take out naturally cooling then; With washing with alcohol, centrifugal,, promptly obtain the nano ferriferrous oxide of modification with the centrifugal powder that obtains in 75 ℃ of vacuum drying ovens dry 25 hours.In second step, in autoclave, put into 30g rac-Lactide, 0.04g tetraphenylporphyrin aluminium alkoxy compound, two (3, the 5-di-t-butyl-4 hydroxybenzyl monoethyl phosphate) nickel of 0.5g, the nano ferriferrous oxide of 4.2g modification, 8.56g THF; Feed nitrogen 5 minutes in the autoclave to remove oxygen, the autoclave lid is tightened put into 170 ℃ baking oven, placed 7 hours; Take out then and use water cooling, open autoclave, pour reaction soln in ethanol post precipitation filtration; And with washing with alcohol deposition 5 times; Suction filtration then, the powder that suction filtration is obtained in 75 ℃ of vacuum drying ovens dry 30 hours promptly obtain POLYACTIC ACID-ferriferrous oxide nano matrix material.
Claims (12)
1. the preparation method of POLYACTIC ACID-ferriferrous oxide nano matrix material is characterized in that, comprises the steps:
The first step, the preparation of modified Nano Z 250:
A, in weight part, in autoclave, add 20～80 parts of nano ferriferrous oxides, 1～25 part of coupling agent, 0～10 part of coupling agent hydrolytic accelerating agent and 15～50 parts of solvents 1, said solvent 1 is one or more in THF, the alcohol organic solvent;
B, before reaction, feed nitrogen in the autoclave to remove oxygen, sealing places reaction constant temperature under, takes out reactant afterwards, cools off;
C, open autoclave, product carries out after with said solvent 1 washing centrifugal, and drying promptly obtains the nano ferriferrous oxide after the modification.
Second step, POLYACTIC ACID-ferriferrous oxide nano Composite Preparation:
A, in weight part; In autoclave, add nano ferriferrous oxide and 25～60 parts of solvents 2 after 25～70 parts rac-Lactide, 0.05～1 part catalyzer, 0～5 part of stablizer, 1～20 part of the first step modification, said solvent 2 is one or more in THF, ketone, halogenated hydrocarbon, the aromatic hydrocarbons organic solvent;
B, before reaction, feed nitrogen in the autoclave to remove oxygen, sealing places reaction constant temperature under, takes out reactant afterwards, cools off;
C, open autoclave, pour reaction soln in ethanol sedimentation and filtration, and with the washing with alcohol deposition until washing out unreacted reactant fully, suction filtration then, drying promptly obtains POLYACTIC ACID-ferriferrous oxide nano matrix material.
2. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material is characterized in that, the particle size of nano ferriferrous oxide is 10～200nm described in the first step step a.
3. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material is characterized in that, coupling agent described in the first step step a is silane coupling agent, titante coupling agent or both mixtures.
4. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material is characterized in that, coupling agent hydrolytic accelerating agent described in the first step step a is acetic acid, hydrochloric acid, organotin or combination in twos.
5. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material is characterized in that, alcohol organic solvent is ethanol, methyl alcohol and Virahol described in the first step step a.
6. according to the preparation method of the said POLYACTIC ACID of claim 1-ferriferrous oxide nano matrix material; It is characterized in that; Place described in the first step step b to react under the constant temperature to be specially, reaction kettle is placed in 80～180 ℃ of thermostat containers, reacted 3～8 hours.
7. according to the preparation method of the said POLYACTIC ACID of claim 1-ferriferrous oxide nano matrix material, it is characterized in that drying is specially described in the first step step c: with the centrifugal powder that obtains in 60～90 ℃ of vacuum drying ovens dry 12～36 hours.
8. according to the preparation method of the said POLYACTIC ACID of claim 1-ferriferrous oxide nano matrix material; It is characterized in that catalyzer described in the second rapid step by step a is one or more the mixture in tetravalence alkyl alkoxy tin, tetravalence tin aryl SnAr2, stannous salt, magnesium complex, aluminum alkyls, aluminum alkoxide, the zinc complex.
9. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material is characterized in that, stablizer is 2 described in the second rapid step by step a; 6-ditertbutylparacresol, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, two (2,2,6; 6-tetramethyl--4-sebate, Tyox B, β-(3; The 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, N '-two-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group) hexanediamine, 4; The mixture of one or more in 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), two (3,5-di-t-butyl-4 hydroxybenzyl monoethyl phosphate) nickel.
10. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material; It is characterized in that; Organic solvent of ketone is acetone, butanone, pimelinketone, toluene pimelinketone and mibk described in the second rapid step by step a, and said halogenated hydrocarbon organic solvent is 1,2-ethylene dichloride, 1; 2-methylene dichloride, chloroform and tetracol phenixin, said aromatic hydrocarbons organic solvent is toluene, benzene and YLENE.
11. the preparation method of POLYACTIC ACID according to claim 1-ferriferrous oxide nano matrix material; It is characterized in that; Placing described in the second rapid step by step b reacted constant temperature under and is specially, and reaction kettle is placed in 120～200 ℃ of thermostat containers, reacts 5～12 hours.
12. the preparation method according to the said POLYACTIC ACID of claim 1-ferriferrous oxide nano matrix material is characterized in that, drying is specially described in the second rapid step by step c: the powder that suction filtration is obtained in 60～90 ℃ of vacuum drying ovens dry 12～36 hours.
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