CN103203881A - Self-reinforced bionic material and manufacture method thereof - Google Patents
Self-reinforced bionic material and manufacture method thereof Download PDFInfo
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Abstract
The invention discloses a self-reinforced bionic material, comprising a reinforced phase prepared from a biodegradable polymer A with high molecular weight and high crystallinity, and a matrix resin phase prepared from a biodegradable polymer B with molecular weight and crystallinity lower than those of the biodegradable polymer A; the reinforced phase and the matrix resin phase are stacked by a guide die; and the stacking percentage of the reinforced phase is 30-90%, and the stacking percentage of the matrix resin phase is 5-60%. The invention also provides a manufacturing method of the self-reinforced bionic material. The invention employs ultrasonic transient heating and interface mechanism with controllable strength to solve a problem for keeping melting fiber morphology when the difference of melting temperature between matrix and the reinforced phase is small; and fiber distribution gradient is constructed to prepare a biodegradable self-reinforced biomimetic material with bamboo imitation structure, high strength and high toughness.
Description
Technical field
The present invention relates to the medical material technology, is a kind of self-reinforcing biomimetic material and manufacture method thereof specifically.
Background technology
Performance such as polylactic acid poly and polyglycolic acid safety, degradable biological material, now in human tissue engineering, body medical domain such as suture, surgibone section material be able to extensive use.But the PLA degradation in vivo is also discharged with metabolite, thereby the misery that makes the patient exempt second operation is used in vivo and had irreplaceable advantage.Yet there are defectives such as initial mechanical intensity is low, poor toughness in PLA when the application of alternative metals material.
Adopt the self-reinforcing technology can effectively improve intensity and the toughness of material, be expected to solve the low and not good problem of toughness of degradable high polymer material initial strength at the medical domain material.The self-reinforcing technology is by changing the aggregated structure of polymer, big molecule is arranged in order along stress direction, under the certain situation of chemical bond energy, effectively improve macroscopical intensity of material, orderly arrangement by strand simultaneously improves degree of crystallinity, thereby reaches the purpose of the further raising strength of materials.
Compare with traditional glass fiber reinforced materials, the wild phase of self-reinforced material and the chemical composition of matrix are identical, take full advantage of the potentiality of material internal, and do not existed wild phase to be combined problem with the interface of matrix on chemical constitution, thereby made the more excellent new material of combination property.Because reinforcing material non-degradables such as glass and charcoal fibers, for use at inside of human body, require the degradable biological medical material, the self-reinforcing The Application of Technology is significant.
At present, the self-reinforcing process of bio-medical material mainly contains following several: fusion co-extrusion, collection of filaments mold pressing, melt impregnation, solution impregnation and solid-state extrude etc., wherein collection of filaments mold pressing is the technology of present comparative maturity.
Collection of filaments compression molding can be adopted different processing methods: mix high polymer molten (1) with the fiber of same material, melt-fibre blend is fast cooling shaping in mould; (2) polymer fiber is arranged in parallel in mould, heating makes its surface melting and bonding under the certain pressure, again cooling forming; (3) levigate polymer powder is mixed with fiber, heating makes powder smelting and a fiber surface melting under the certain pressure, and internal approach is constant, again cooling forming.
The key that adopts fine bundle mould pressing technology to prepare self-reinforced material is fully to coat wild phase and keep the wild phase fibre morphology intact after the matrix fusion.Both melt temperature differences are big greatly as far as possible mutually with fiber to require matrix resin generally speaking, and actual process window is very narrow, and processing HTHP border is favourable for the adhesion of improving the two, yet the orientation of damage structure, deterioration in material properties are arranged; Low-temp low-pressure is effectively in keeping good orientation texture, yet may cause between the fiber or the adhesion deficiency of fiber between matrix, exists the matrix fusion to need high temperature and the wild phase form keeps requiring the contradiction of low temperature.
The pressure that solid is extruded is cold drawn to exist that process window is narrow, production efficiency is low and deficiency such as performance inconsistency is big.Batch production not only is difficult to satisfy the demand of producing in enormous quantities, and stable also being difficult to of properties of product guarantees, can't satisfy high-quality, the stable performance requirement of using material in the human body body.
Summary of the invention
The objective of the invention is to overcome the deficiency that above prior art exists, the interface interaction mechanism of the moment heating of using ultrasound ripple, controllable intensity, the fusion and the fibre morphology that solve under matrix and the less situation of wild phase melt temperature difference keep a difficult problem, prepare the biodegradable self-reinforcing biomimetic material of a kind of imitative bamboo structure high strength, high tenacity by structure fiber distribution gradient.
Another purpose of the present invention is to provide a kind of manufacture method of self-reinforcing biomimetic material.
In order to achieve the above object, the present invention is by the following technical solutions: a kind of self-reinforcing biomimetic material comprises the matrix resin of the biodegradable polymers B preparation that all is lower than described biodegradable polymers A by the wild phase of the biodegradable polymers A preparation of HMW, high-crystallinity, by molecular weight and degree of crystallinity mutually; Wherein, wild phase piles up the mass percent 30～90% that wild phase piles up, the mass percent 5～60% that matrix resin piles up mutually with matrix resin by the guiding mould.
The wild phase of described biodegradable polymers A preparation is biodegradable polymers fiber or nonwoven; The biodegradable polymers A of described HMW, high-crystallinity is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid or the poly-dioxane.
The matrix resin of described biodegradable polymers B preparation is biodegradable polymers film, nonwoven or fiber mutually; Described biodegradable polymers B is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid or the poly-dioxane.
The number-average molecular weight of described wild phase 〉=3000, degree of crystallinity 〉=50%.
Described matrix resin phase degree of crystallinity≤50%.
Preferably,The number-average molecular weight of described wild phase 〉=5000, degree of crystallinity 〉=60%, matrix resin phase degree of crystallinity≤40%, the mass percent 50～90% that wild phase piles up, the mass percent 10～50% that matrix resin piles up mutually.
A kind of manufacture method of self-reinforcing biomimetic material may further comprise the steps:
(1), the biodegradable polymers A by HMW, high-crystallinity prepares wild phase;
(2), by molecular weight and degree of crystallinity all be lower than biodegradable polymers A in the step (1) biodegradable polymers B preparation matrix resin mutually;
(3), get wild phase mass percent 30～90%, the mixture of matrix resin phase mass percent 5～60%, mixture are put into the guiding mould and are piled up;
(4), pile up carry out compression molding after finishing or ultrasonic continuous compound.
The wild phase of the biodegradable polymers A preparation in the described step (1) is biodegradable polymers fiber or nonwoven; The biodegradable polymers A of described HMW, high-crystallinity is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid, the poly-dioxane etc., and the matrix resin of the biodegradable polymers B preparation in the described step (2) is biodegradable polymers film, nonwoven or fiber mutually; Described biodegradable polymers B is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid, the poly-dioxane etc.
Number-average molecular weight 〉=3000, degree of crystallinity 〉=50% of wild phase in the described step (1), matrix resin phase degree of crystallinity in the step (2)≤50%.
Preferably, the number-average molecular weight of described wild phase 〉=5000, degree of crystallinity 〉=60%, matrix resin phase degree of crystallinity≤40%, the mass percent 50～90% that wild phase piles up, the mass percent 10～50% that matrix resin piles up mutually.
Described guiding mould comprises the guiding die ontology, offer some groove and/or holes for matrix phase or wild phase guiding and location on the guiding die ontology, groove is rectangle laterally, and groove is vertically arranged, the height of groove is 0.1 ~ 5mm, and vertically the spacing of adjacent slot is 1 ~ 3mm; Bore dia 0.01 ~ 3mm piles up by groove and the hole gradient that realizes fiber that is staggered, and the two mass percent of flexible modulation.
The compound employing ultrasonic welding machine of described ultrasonic continuous carries out, and can adopt step compression molding and composite molding continuously, and composite molding realizes by design automatic feeder and material collecting device continuously.
The present invention has following advantage and effect with respect to prior art:
1, the present invention in the preparation of self-reinforced material, solves the ultrasonic applications of ultrasonic wave moment heating, controllable intensity matrix resin phase and wild phase and carry out a compound difficult problem under the little situation of melt temperature difference.
2, the present invention is by the distribution gradient of guiding mold structure wild phase, and wild phase piles up mutually with matrix resin, has excellent flexibility and adaptability widely at the biodegradable medical bionics material of preparation high-strength and high ductility.
3, the present invention overcome collection of filaments compression molding can only batch (-type), the shortcoming of can not serialization producing, production efficiency significantly improves, properties of product are more stable.
The specific embodiment
The present invention is described in further detail for ease of it will be appreciated by those skilled in the art that following embodiment.
Embodiment 1:
Select two kinds of PLAs (code name is A and B) that molecular weight is different with degree of crystallinity, A is that number-average molecular weight is 100000 PLLA, degree of crystallinity 70%; B is that number-average molecular weight is 60000 meso PLA, degree of crystallinity 30%.
(1) adopt melt spinning method to prepare the long fibre of PLA A, fibre fineness is 6D;
(2) adopt the blown film legal system to be equipped with PLA B film, film thickness is 15um;
(3) by guiding mould with the long fibre of mass percent 60% and 40% stacks of thin films;
(4) it is compound to adopt ultrasonic welding machine that stack material is carried out continuously, and ultrasonic power 3KW, speed of production 10m/min make the self-reinforcing poly-lactic acid material.
The above-mentioned material normal temperature condition carries out performance test after placing 24h naturally, and hot strength is that 186MPa, elongation at break are 46%, impact flexibility 15.3KJ/m
2
Embodiment 2～6
Select the molecular weight PLA different with degree of crystallinity, prepare different wild phase and continuous phase, complex method is with embodiment 1, following table as a result.
Embodiment 7
Select two kinds of polyglycolic acids (code name is D and E) that molecular weight is different with degree of crystallinity, the number-average molecular weight 100000 of D, degree of crystallinity 70%; E is that number-average molecular weight is 50000, degree of crystallinity 40%.
(1) adopt melt spinning method to prepare the nonwoven of polyglycolic acid D, grammes per square metre is 40g/m
2
(2) adopt The tape casting to prepare the film of polyglycolic acid E, film thickness is 15um;
(3) by guiding mould with the nonwoven of mass percent 60% and 40% stacks of thin films;
(4) it is compound to adopt ultrasonic welding machine that stack material is carried out continuously, and ultrasonic power 3KW, speed of production 12m/min make self-reinforcing polyglycolic acid material.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 380MPa, elongation at break are 24%, impact flexibility 9.1KJ/m
2
Embodiment 8～12
Select the molecular weight polyglycolic acid different with degree of crystallinity, prepare different wild phase and continuous phase, complex method is with embodiment 7, following table as a result.
Embodiment 13
Select two kinds of poly-beta-hydroxy-butanoic acids (PHB) (code name is F and G) that molecular weight is different with degree of crystallinity, the number-average molecular weight 50000 of F, degree of crystallinity 60%; The number-average molecular weight of G is 40000, degree of crystallinity 40%.
(1) adopt melt spinning method to prepare the long fibre of F, fibre fineness is 10D;
(2) adopt melt spinning method to prepare the long fibre of G, fibre fineness is 10D;
(3) by the guiding mould F long fibre of mass percent 60% and 40% G long fibre are piled up;
(4) it is compound to adopt ultrasonic welding machine that stack material is carried out continuously, and ultrasonic power 3KW, speed of production 10m/min make the poly-beta-hydroxy-butanoic acid material of self-reinforcing.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 122MPa, elongation at break are 135%, impact flexibility 18.5KJ/m
2
Embodiment 14～18
Select the molecular weight poly-beta-hydroxy-butanoic acid different with degree of crystallinity, prepare different wild phase and continuous phase, complex method is with embodiment 13, following table as a result.
Embodiment 19
The material of matrix and wild phase and preparation method adopt ultrasonic welding machine that stack material is carried out the boundling compression molding with embodiment 1, and pressure 0.8MPa, time 0.5S make the self-reinforcing poly-lactic acid material.
The above-mentioned material normal temperature condition carries out performance test after placing 24h naturally, and hot strength is that 195MPa, elongation at break are 43%, impact flexibility 15.8KJ/m
2
Embodiment 20
The material of matrix and wild phase and preparation method adopt ultrasonic welding machine that stack material is carried out the boundling compression molding with embodiment 7, and pressure 0.9MPa, time 0.6S make self-reinforcing polyglycolic acid material.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 384MPa, elongation at break are 25%, impact flexibility 9.6KJ/m
2
Embodiment 21
The material of matrix and wild phase and preparation method adopt ultrasonic welding machine that stack material is carried out the boundling compression molding with embodiment 13, and pressure 1.2MPa, time 0.3S make the poly-beta-hydroxy-butanoic acid material of self-reinforcing.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 126MPa, elongation at break are 142%, impact flexibility 18.2KJ/m
2
Embodiment 22
Select two kinds of polylactic acid-glycolic guanidine-acetic acid copolymers (PLGA) (code name is H and I) that molecular weight is different with degree of crystallinity, the number-average molecular weight 80000 of H, degree of crystallinity 60%; The number-average molecular weight of I is 60000, degree of crystallinity 40%.
(1) adopt melt spinning method to prepare the long fibre of H, fibre fineness is 10D;
(2) employing blown film legal system is equipped with the film of I, thickness 15um;
(3) by guiding mould with the H long fibre of mass percent 60% and 40% I stacks of thin films;
(4) it is compound to adopt ultrasonic welding machine that stack material is carried out continuously, and ultrasonic power 3KW, speed of production 10m/min make self-reinforcing PLGA material.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 325MPa, elongation at break are 28%, impact flexibility 11.3KJ/m
2
Embodiment 23
Select two kinds of poly-dioxane (code name is J and K) that molecular weight is different with degree of crystallinity, the number-average molecular weight 75000 of J, degree of crystallinity 65%; The number-average molecular weight of K is 50000, degree of crystallinity 30%.
(1) the employing melt spinning method prepares the nonwoven of J, grammes per square metre 30g/m
2
(2) the employing The tape casting prepares the film of K, thickness 16um;
(3) by the guiding mould K of mass percent 70% and 30% K are piled up;
(4) it is compound to adopt ultrasonic welding machine that stack material is carried out continuously, and ultrasonic power 3KW, speed of production 10m/min make the poly-dioxane material of self-reinforcing.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 375MPa, elongation at break are 76%, impact flexibility 16.9KJ/m
2
Comparative Examples 1
The material of matrix and wild phase and preparation method adopt flat-bed press that stack material is carried out the boundling compression molding with embodiment 1, and 5 minutes preheating time, hot pressing 1 minute, make the self-reinforcing poly-lactic acid material at 2 minutes cool times.
The above-mentioned material normal temperature condition carries out performance test after placing 24h naturally, and hot strength is that 75MPa, elongation at break are 32%, impact flexibility 10.2KJ/m
2
Comparative Examples 2
The material of matrix and wild phase and preparation method adopt flat-bed press that stack material is carried out the boundling compression molding with embodiment 4, and 5 minutes preheating time, hot pressing 1 minute, make self-reinforcing polyglycolic acid material at 2 minutes cool times.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 152MPa, elongation at break are 18%, impact flexibility 7.9KJ/m
2
Comparative Examples 3
The material of matrix and wild phase and preparation method adopt flat-bed press that stack material is carried out the boundling compression molding with embodiment 5, and 5 minutes preheating time, hot pressing 1 minute, make the poly-beta-hydroxy-butanoic acid material of self-reinforcing at 2 minutes cool times.
The above-mentioned material normal temperature condition is tested after placing 24h naturally, and hot strength is that 46MPa, elongation at break are 153%, impact flexibility 15.5KJ/m
2
From as can be known above-mentioned, adopt the ultrasonic wave combination process to have to strengthen effective, speed fast, need not preheating and cooling, advantage such as can produce continuously.
The above-mentioned specific embodiment is the preferred embodiments of the present invention, can not limit the present invention, and other any change or other equivalent substitute mode that does not deviate from technical scheme of the present invention and make is included within protection scope of the present invention.
Claims (10)
1. a self-reinforcing biomimetic material is characterized in that: comprise the matrix resin of the biodegradable polymers B preparation that all is lower than described biodegradable polymers A by the wild phase of the biodegradable polymers A preparation of HMW, high-crystallinity, by molecular weight and degree of crystallinity mutually; Wherein, wild phase piles up the mass percent 30～90% that wild phase piles up, the mass percent 5～60% that matrix resin piles up mutually with matrix resin by the guiding mould.
2. self-reinforcing biomimetic material according to claim 1 is characterized in that: the wild phase of described biodegradable polymers A preparation is biodegradable polymers fiber or nonwoven; The biodegradable polymers A of described HMW, high-crystallinity is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid or the poly-dioxane.
3. self-reinforcing biomimetic material according to claim 1 is characterized in that: the matrix resin of described biodegradable polymers B preparation is biodegradable polymers film, nonwoven or fiber mutually; Described biodegradable polymers B is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid or the poly-dioxane.
4. self-reinforcing biomimetic material according to claim 1 is characterized in that: the number-average molecular weight of described wild phase 〉=3000, degree of crystallinity 〉=50%.
5. self-reinforcing biomimetic material according to claim 1 is characterized in that: described matrix resin phase degree of crystallinity≤50%.
6. self-reinforcing biomimetic material according to claim 1, it is characterized in that: the number-average molecular weight of described wild phase 〉=5000, degree of crystallinity 〉=60%, matrix resin phase degree of crystallinity≤40%, the mass percent 50～90% that wild phase piles up, the mass percent 10～50% that matrix resin piles up mutually.
7. the manufacture method of a self-reinforcing biomimetic material is characterized in that, may further comprise the steps:
(1), the biodegradable polymers A by HMW, high-crystallinity prepares wild phase;
(2), by molecular weight and degree of crystallinity all be lower than biodegradable polymers A in the step (1) biodegradable polymers B preparation matrix resin mutually;
(3), get wild phase mass percent 30～90%, the mixture of matrix resin phase mass percent 5～60%, mixture are put into the guiding mould and are piled up;
(4), pile up carry out compression molding after finishing or ultrasonic continuous compound.
8. the manufacture method of self-reinforcing biomimetic material according to claim 7 is characterized in that: the wild phase of the biodegradable polymers A preparation in the described step (1) is biodegradable polymers fiber or nonwoven; The biodegradable polymers A of described HMW, high-crystallinity is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid, the poly-dioxane, and the matrix resin of the biodegradable polymers B preparation in the described step (2) is biodegradable polymers film, nonwoven or fiber mutually; Described biodegradable polymers B is a kind of in polyglycolic acid, PLA, polylactic acid-glycolic guanidine-acetic acid copolymer, poly-β-hydroxybutyric acid, the poly-dioxane.
9. the manufacture method of self-reinforcing biomimetic material according to claim 7 is characterized in that: number-average molecular weight 〉=3000, degree of crystallinity 〉=50% of wild phase in the described step (1), matrix resin phase degree of crystallinity in the step (2)≤50%.
10. the manufacture method of self-reinforcing biomimetic material according to claim 7, it is characterized in that: the number-average molecular weight of described wild phase 〉=5000, degree of crystallinity 〉=60%, matrix resin phase degree of crystallinity≤40%, the mass percent 50～90% that wild phase piles up, the mass percent 10～50% that matrix resin piles up mutually.
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| CN106346776A (en) * | 2016-09-13 | 2017-01-25 | 复旦大学 | Superposition printing structure and method for 3D printing products of homogeneous or heterogeneous materials |
| CN106671545A (en) * | 2016-11-08 | 2017-05-17 | 江南大学 | High-fiber volume content polylactic acid homopolymer composite material and preparation method thereof |
| CN107718813A (en) * | 2017-09-26 | 2018-02-23 | 江南大学 | A kind of high-performance fiber base all-polymer composite board and preparation method thereof |
| CN109651774A (en) * | 2018-12-21 | 2019-04-19 | 付传英 | A kind of Biodegradable medical material and preparation method thereof |
| CN114875574A (en) * | 2022-05-23 | 2022-08-09 | 江南大学 | High-strength high-modulus polyvinyl alcohol fiber reinforced polylactic acid composite material and preparation method thereof |
| CN115028862A (en) * | 2022-07-18 | 2022-09-09 | 南通大学 | Environment-friendly polylactic acid self-reinforced composite material and preparation method thereof |
| CN115157651A (en) * | 2022-08-19 | 2022-10-11 | 西安交通大学 | Bionic editing method of semi-crystalline polymer material polymer chain and bionic editing method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106346776A (en) * | 2016-09-13 | 2017-01-25 | 复旦大学 | Superposition printing structure and method for 3D printing products of homogeneous or heterogeneous materials |
| CN106671545A (en) * | 2016-11-08 | 2017-05-17 | 江南大学 | High-fiber volume content polylactic acid homopolymer composite material and preparation method thereof |
| CN106671545B (en) * | 2016-11-08 | 2019-04-09 | 江南大学 | A kind of high microsteping volume content polylactic acid list polymer composites and preparation method thereof |
| CN107718813A (en) * | 2017-09-26 | 2018-02-23 | 江南大学 | A kind of high-performance fiber base all-polymer composite board and preparation method thereof |
| CN107718813B (en) * | 2017-09-26 | 2019-07-23 | 江南大学 | A kind of high-performance fiber base all-polymer composite board and preparation method thereof |
| CN109651774A (en) * | 2018-12-21 | 2019-04-19 | 付传英 | A kind of Biodegradable medical material and preparation method thereof |
| CN114875574A (en) * | 2022-05-23 | 2022-08-09 | 江南大学 | High-strength high-modulus polyvinyl alcohol fiber reinforced polylactic acid composite material and preparation method thereof |
| CN114875574B (en) * | 2022-05-23 | 2024-01-19 | 江南大学 | High-strength high-modulus polyvinyl alcohol fiber reinforced polylactic acid composite material and preparation method thereof |
| CN115028862A (en) * | 2022-07-18 | 2022-09-09 | 南通大学 | Environment-friendly polylactic acid self-reinforced composite material and preparation method thereof |
| CN115028862B (en) * | 2022-07-18 | 2024-04-09 | 南通大学 | Environment-friendly polylactic acid self-reinforced composite material and preparation method thereof |
| CN115157651A (en) * | 2022-08-19 | 2022-10-11 | 西安交通大学 | Bionic editing method of semi-crystalline polymer material polymer chain and bionic editing method |
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| CN103203881B (en) | 2015-08-05 |
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