CN104275883A - Nanofiber reinforced polylactic acid/polycaprolactone composite material and preparation method thereof - Google Patents
Nanofiber reinforced polylactic acid/polycaprolactone composite material and preparation method thereof Download PDFInfo
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- CN104275883A CN104275883A CN201310278728.6A CN201310278728A CN104275883A CN 104275883 A CN104275883 A CN 104275883A CN 201310278728 A CN201310278728 A CN 201310278728A CN 104275883 A CN104275883 A CN 104275883A
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- polycaprolactone
- polylactic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
Abstract
The invention relates to a nanofiber reinforced polylactic acid/polycaprolactone composite material and a preparation method thereof. The preparation method comprises the following steps: magnetically stirring polylactic acid and polycaprolactone, adding the obtained mixture into an electrostatic spinning device, carrying out electrostatic spinning, drying to obtain electrospinned fiber reinforcement sheets and polycaprolactone sheets, superposing the electrospinned fiber reinforcement sheets and polycaprolactone sheets according to a layer-by-layer structure, carrying out compression molding through a hydraulic molding machine, and carrying out cold pressing through a vulkameter. The polylactic acid/polycaprolactone blend electrospinned fibers are tightly combed with the a polycaprolactone matrix, so the mechanical strength of the prepared composite material is good, the tensile strength of the composite material reaches above 24MPa, the cantilever beam notch impact strength of the composite material reaches above 59MPa, the flexural modulus of the composite material reaches above 878MPa, and the mechanical performances of the composite material are obviously better than those of present products. The polylactic acid/polycaprolactone composite material has widened uses, and can be widely used in the field of biodegradable plastics.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to polylactic acid and caprolactone composite of a kind of nanofiber enhancing and preparation method thereof.
Background technology
The method of modifying of fiber-reinforced polymer material is all widely known by the people in academia or industrial quarters.Traditional inorganic fibrous fillers, if its size such as glass fibre, carbon fiber is usually more than ten microns, good being dispersed in polymeric matrix can form micron order composite.If but can fiber size be reduced, will the interfacial area of increased fiber and substrate contact be conducive to, thus promote the macro property of composite further.Electrostatic spinning is a kind of efficient method easily reducing fiber size.
PLA (following abbreviation PLA) can derive from renewable resource completely, thoroughly broken away from the dependence to petroleum resources, it also has, and glossiness be high, transparency is high, resilience and curling persistence is good, grease resistance and dyeability is good, flammable low, to advantages such as human non-toxic's evils.
Polycaprolactone (following abbreviation PCL) is a kind of thermoplastic of microbial degradation type, have good biological degradability and good mechanical property, it is widely used as medical Modeling Material, industry, art modelling material, toy, toner, hot copying ink adhesive agent, PUR mixture etc.
But PLA (PLA) and polycaprolactone (PCL) are all relative with toughness than the intensity of the petroleum base engineering plastics of current industrial extensive use poor, thus greatly limit their extensive use.
PLA/PCL blend fibers combines with PCL matrix by the present invention, when PLA/PCL blend fibers and PCL matrix at higher than PCL fusing point but lower than the temperature of PLA fusing point through hot binding time, the PCL component of fiber surface can merge with matrix PCL, namely PCL matrix " can embed " the even more depths, top layer of fiber, this is just equivalent to the specific area adding fiber, strengthen the bonding of fiber and matrix, namely the PCL component in blend fibers can serve as the role of " adhesive ", fiber and matrix are combined closely, make the Compound Material Engineering intensity of preparation good, of many uses.
Summary of the invention
The object of this invention is to provide polylactic acid and caprolactone composite of a kind of nanofiber enhancing and preparation method thereof, the preparation method of this composite is simple, and makes the composite obtained have good mechanical property.
A preparation method for the polylactic acid and caprolactone composite that nanofiber strengthens, comprises the following steps:
(1) PLA 30-40 part and polycaprolactone 60-70 part are dissolved in a solvent, magnetic agitation 2-20h, obtains uniform spinning solution;
(2) spinning solution is added in electrostatic spinning apparatus, switches on power, under 10-20KV voltage, carry out electrostatic spinning, fiber drawn, solvent volatilize and after solidifying Direct precipitation on the dash receiver of polycaprolactone matrix, dry electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 90-110 part and polycaprolactone sheet material 40-60 part with layer-by-layer type folded structures, after compressing with hydraulic forming machine, vulcameter is colded pressing under room temperature condition 1-10min, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
In described step (1), solvent is chloroform and dimethyl formamide is 2:3 composition by weight.
In described step (2), drying refers to vacuum drying 20-24h at 50-80 DEG C.
The temperature of hydraulic forming machine is 100-150 DEG C in described step (3), pressure is 10-20Mpa, the press time is 5-10min.
Another object of the present invention is to provide the polylactic acid and caprolactone composite of nanofiber enhancing prepared by a kind of aforementioned preparation process.
Electrostatic spinning is a kind of method that polymeric hardener becomes fiber, refers to the special shape of polymeric fluid electrostatic atomization, and now the material is divided in atomization is not fine droplet, but the small jet of polymer, quite long distance can be run, be finally solidified into fiber.
Electrostatic spinning apparatus is with the syringe of 0.01-0.1mm internal diameter syringe needle and receiving system to form.
In the present invention, the detailed process of electrostatic spinning is: added by spinning solution in the syringe of band 0.01-0.1mm internal diameter syringe needle, the positive pole of power supply inserts in this solution or is connected with syringe needle, the negative pole of power supply is connected with the receiving system preparing ordered fiber, and spinning solution at the uniform velocity flows out under the propelling of micro-injection pump.After good Distance geometry solution flow rate between needle point and receiving system to be regulated, switch on power, under 10-20KV voltage, carry out electrostatic spinning, after the volatilization of fiber drawn, solvent, solidification, Direct precipitation is on receiving system, the dash receiver of receiving system to be polycaprolactone be matrix.Sediment is vacuum drying 20-24h at 50 DEG C-80 DEG C, allows residual solvent volatilize completely completely, obtains electrospinning fibre reinforcement sheet material.
In the present invention, " layer-by-layer type " folded structures is known stepped construction, namely refers to successively superpose and the structure formed.By the electrospinning fibre reinforcement sheet material of some and polycaprolactone sheet material according to one deck electrospinning fibre reinforcement sheet material, the superposition of one deck polycaprolactone sheet and the structure plate, again one deck electrospinning fibre reinforcement sheet material that are formed successively in the present invention
PLA (PLA) and polycaprolactone (PCL) blend are carried out the fiber that electrostatic spinning becomes to be punctured in the lamellar structure of polycaprolactone (PCL) matrix as reinforcement with laminated by the present invention, this fiber is distributed in PCL matrix preferably with modification PCL matrix, then PLA and PCL is utilized to there is larger difference in melt temperature, at the temperature higher than PCL fusing point lower than PLA fusing point, obtain composite through hot pressing.Because the PCL component of fiber surface can merge with matrix PCL, make PCL matrix " can embed " the even more depths, top layer of fiber, this is just equivalent to the specific area adding fiber, strengthens the bonding of fiber and matrix.PCL component in blend fibers act as the role of " adhesive ", fiber and PCL matrix are combined closely, make the Compound Material Engineering intensity of preparation good, its hot strength reaches 24 more than MPa, Izod notched impact strength reaches 59 more than MPa, and bending modulus reaches 878 more than MPa, apparently higher than the mechanical performance of existing product, and expanded the purposes of polylactic acid and caprolactone composite, can be widely used in biodegradable plastic field.
The polylactic acid and caprolactone that nanofiber strengthens meets the new way that material is fibre reinforced composites industry development, has larger potential using value.PLA and PCL blend add the physical property that improve composite, expand the application of material.
Detailed description of the invention
Below in conjunction with specific embodiment, one detailed elaboration is done to the present invention.
The present invention adopts polylactic acid PLA/polycaprolactone (PCL) blend electrospun fiber membrane to be punctured in the lamellar structure of PCL matrix as reinforcement with laminated, fiber is distributed in PCL matrix preferably with modification PCL matrix, then utilize PLA and PCL to there is larger difference in melt temperature, obtain composite through hot pressing.The complex solvent preparing blend electrospinning fibre is the chloroform (CHCL of two parts
3) and the dimethyl formamide (C of three parts
3h
7nO) formulated.
Embodiment 1
(1) be dissolved in by PLA 30 parts and polycaprolactone 70 parts by chloroform and dimethyl formamide by weight in the solvent formed for 2:3, magnetic agitation 2h, obtains uniform spinning solution;
(2) added by spinning solution in the syringe of band 0.01mm internal diameter syringe needle, the positive pole of power supply inserts in this solution, and the negative pole of power supply is connected with the receiving system preparing ordered fiber, and spinning solution at the uniform velocity flows out under the propelling of micro-injection pump; After good Distance geometry solution flow rate between needle point and receiving system to be regulated, switch on power, under 10KV voltage, carry out electrostatic spinning, after the volatilization of fiber drawn, solvent, solidification, Direct precipitation is on receiving system, the dash receiver of receiving system to be polycaprolactone be matrix.Sediment is vacuum drying 20h at 50 DEG C, allows residual solvent volatilize completely completely, obtains electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 100 parts and polycaprolactone sheet material 50 parts with layer-by-layer type folded structures, temperature be 100 DEG C, pressure suppresses 5min with hydraulic forming machine under being 10Mpa, cold pressing after shaping 1min on vulcameter under room temperature condition, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
Embodiment 2:
(1) be dissolved in by PLA 30 parts and polycaprolactone 60 parts by chloroform and dimethyl formamide by weight in the solvent formed for 2:3, magnetic agitation 12h, obtains uniform spinning solution;
(2) added by spinning solution in the syringe of band 0.1mm internal diameter syringe needle, the positive pole of power supply inserts in this solution, and the negative pole of power supply is connected with the receiving system preparing ordered fiber, and spinning solution at the uniform velocity flows out under the propelling of micro-injection pump; After good Distance geometry solution flow rate between needle point and receiving system to be regulated, switch on power, under 12KV voltage, carry out electrostatic spinning, after the volatilization of fiber drawn, solvent, solidification, Direct precipitation is on receiving system, the dash receiver of receiving system to be polycaprolactone be matrix.Sediment is vacuum drying 24h at 80 DEG C, allows residual solvent volatilize completely completely, obtains electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 90 parts and polycaprolactone sheet material 40 parts with layer-by-layer type folded structures, temperature be 150 DEG C, pressure suppresses 10min with hydraulic forming machine under being 20Mpa, cold pressing after shaping 10min on vulcameter under room temperature condition, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
Embodiment 3
(1) be dissolved in by PLA 40 parts and polycaprolactone 70 parts by chloroform and dimethyl formamide by weight in the solvent formed for 2:3, magnetic agitation 20h, obtains uniform spinning solution;
(2) added by spinning solution in the syringe of band 0.1mm internal diameter syringe needle, the positive pole of power supply is connected with syringe needle, and the negative pole of power supply is connected with the receiving system preparing ordered fiber, and spinning solution at the uniform velocity flows out under the propelling of micro-injection pump; After good Distance geometry solution flow rate between needle point and receiving system to be regulated, switch on power, under 20KV voltage, carry out electrostatic spinning, after the volatilization of fiber drawn, solvent, solidification, Direct precipitation is on receiving system, the dash receiver of receiving system to be polycaprolactone be matrix.Sediment is vacuum drying 24h at 50 DEG C, allows residual solvent volatilize completely completely, obtains electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 110 parts and polycaprolactone sheet material 60 parts with layer-by-layer type folded structures, temperature be 120 DEG C, pressure suppresses 6min with hydraulic forming machine under being 14Mpa, cold pressing after shaping 5min on vulcameter under room temperature condition, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
Embodiment 4
(1) be dissolved in by PLA 35 parts and polycaprolactone 65 parts by chloroform and dimethyl formamide by weight in the solvent formed for 2:3, magnetic agitation 12h, obtains uniform spinning solution;
(2) added by spinning solution in the syringe of band 0.05mm internal diameter syringe needle, the positive pole of power supply is connected with syringe needle, and the negative pole of power supply is connected with the receiving system preparing ordered fiber, and spinning solution at the uniform velocity flows out under the propelling of micro-injection pump; After good Distance geometry solution flow rate between needle point and receiving system to be regulated, switch on power, under 15KV voltage, carry out electrostatic spinning, after the volatilization of fiber drawn, solvent, solidification, Direct precipitation is on receiving system, the dash receiver of receiving system to be polycaprolactone be matrix.Sediment is vacuum drying 22h at 60 DEG C, allows residual solvent volatilize completely completely, obtains electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 100 parts and polycaprolactone sheet material 60 parts with layer-by-layer type folded structures, temperature be 130 DEG C, pressure suppresses 7min with hydraulic forming machine under being 15Mpa, cold pressing after shaping 5min on vulcameter under room temperature condition, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
Comparative example 1: prepare barium sulfate crystal whisker/PCL composite
Take 10 parts of barium sulfate crystal whiskers and 90 parts of PCL, be pressed into sheet material, then by they with layer-by-layer type folded structures then on hydraulic forming machine with 120 DEG C, lower 6 minutes of pressure 14Mpa is shaping, then on vulcameter, room temperature is colded pressing 5 minutes, obtains composite.
The compound material above-mentioned enforcement 1-4 and comparative example 1 prepared is made batten with injection machine respectively and is tested its hot strength, Izod notched impact strength and bending modulus, and test data is as following table 1.
Wherein: hot strength presses ASTM D 638 standard testing, Izod notched impact strength presses ASTM D256 standard testing, and bending modulus presses ASTM D790 standard testing.
Table 1 material property list
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Hot strength | MPa | 66 | 59 | 63 | 68 | 51 |
| Izod notched impact strength | Mpa | 25.1 | 25.0 | 26.6 | 24.1 | 20.9 |
| Bending modulus | MPa | 878.2 | 1036.4 | 1144.5 | 929.7 | 597.1 |
As can be seen from the above table, compared with barium sulfate crystal whisker/PCL composite prepared by the polylactic acid and caprolactone composite that nanofiber of the present invention the strengthens inorganic fibrous fillers common with the interpolation in comparative example 1, its hot strength reaches 24 more than MPa, Izod notched impact strength reaches 59 more than MPa, bending modulus reaches 878 more than MPa, apparently higher than the mechanical performance of comparative example 1 barium sulfate crystal whisker/PCL composite.Thus greatly extend the application of the polylactic acid and caprolactone composite that nanofiber of the present invention strengthens, can be widely used in biodegradable plastic field.
Be only several specific embodiments of the application above, but the application is not limited thereto, the changes that any person skilled in the art can think of, all should drops in the protection domain of the application.
Claims (5)
1. a preparation method for the polylactic acid and caprolactone composite of nanofiber enhancing, is characterized in that: comprise the following steps:
(1) PLA 30-40 part and polycaprolactone 60-70 part are dissolved in a solvent, magnetic agitation 2-20h, obtains uniform spinning solution;
(2) spinning solution is added in electrostatic spinning apparatus, switches on power, under 10-20KV voltage, carry out electrostatic spinning, fiber drawn, solvent volatilize and after solidifying Direct precipitation on the dash receiver of polycaprolactone matrix, dry electrospinning fibre reinforcement sheet material;
(3) by electrospinning fibre reinforcement sheet material 90-110 part and polycaprolactone sheet material 40-60 part with layer-by-layer type folded structures, after compressing with hydraulic forming machine, vulcameter is colded pressing under room temperature condition 1-10min, obtains the polylactic acid and caprolactone composite that nanofiber strengthens.
2. preparation method according to claim 1, is characterized in that: in described step (1), solvent is that chloroform and dimethyl formamide form by weight for 2:3.
3. preparation method according to claim 1, is characterized in that: in described step (2), drying refers to vacuum drying 20-24h at 50-80 DEG C.
4. preparation method according to claim 1, is characterized in that: in described step (3), the temperature of hydraulic forming machine is 100-150 DEG C, pressure is 10-20Mpa, the press time is 5-10min.
5. the polylactic acid and caprolactone composite that strengthens of the nanofiber prepared of preparation method as claimed in claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310278728.6A CN104275883A (en) | 2013-07-03 | 2013-07-03 | Nanofiber reinforced polylactic acid/polycaprolactone composite material and preparation method thereof |
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|---|---|---|---|
| CN201310278728.6A CN104275883A (en) | 2013-07-03 | 2013-07-03 | Nanofiber reinforced polylactic acid/polycaprolactone composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521722A (en) * | 2015-09-15 | 2017-03-22 | 国网智能电网研究院 | Device for fiber blending |
| CN109847112A (en) * | 2017-11-20 | 2019-06-07 | 山东省药学科学院 | Enhanced absorbable intraluminal stent of one kind and preparation method thereof |
| CN110835807A (en) * | 2019-11-29 | 2020-02-25 | 吉林大学 | Carbon fiber reinforced polyether-ether-ketone fiber composite material and preparation method and application thereof |
| CN111389244A (en) * | 2020-03-10 | 2020-07-10 | 武汉纺织大学 | High-peel-strength nanofiber composite membrane and preparation method thereof |
| CN114751789A (en) * | 2022-02-24 | 2022-07-15 | 吉林大学 | Slow-release fertilizer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1361039A1 (en) * | 2002-05-10 | 2003-11-12 | Board of Trustees of Michigan State University | Environmentally friendly polylactide-based composite formulations |
| CN102862355A (en) * | 2012-10-09 | 2013-01-09 | 扬州大学 | Biodegradable polymer composite and preparation method thereof |
-
2013
- 2013-07-03 CN CN201310278728.6A patent/CN104275883A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1361039A1 (en) * | 2002-05-10 | 2003-11-12 | Board of Trustees of Michigan State University | Environmentally friendly polylactide-based composite formulations |
| CN102862355A (en) * | 2012-10-09 | 2013-01-09 | 扬州大学 | Biodegradable polymer composite and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521722A (en) * | 2015-09-15 | 2017-03-22 | 国网智能电网研究院 | Device for fiber blending |
| CN109847112A (en) * | 2017-11-20 | 2019-06-07 | 山东省药学科学院 | Enhanced absorbable intraluminal stent of one kind and preparation method thereof |
| CN110835807A (en) * | 2019-11-29 | 2020-02-25 | 吉林大学 | Carbon fiber reinforced polyether-ether-ketone fiber composite material and preparation method and application thereof |
| CN111389244A (en) * | 2020-03-10 | 2020-07-10 | 武汉纺织大学 | High-peel-strength nanofiber composite membrane and preparation method thereof |
| CN111389244B (en) * | 2020-03-10 | 2022-10-11 | 武汉纺织大学 | High-peel-strength nanofiber composite membrane and preparation method thereof |
| CN114751789A (en) * | 2022-02-24 | 2022-07-15 | 吉林大学 | Slow-release fertilizer and preparation method thereof |
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