CN106519616A - Fiber-reinforced polylactic acid compound and preparation method thereof - Google Patents
Fiber-reinforced polylactic acid compound and preparation method thereof Download PDFInfo
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- CN106519616A CN106519616A CN201611015129.5A CN201611015129A CN106519616A CN 106519616 A CN106519616 A CN 106519616A CN 201611015129 A CN201611015129 A CN 201611015129A CN 106519616 A CN106519616 A CN 106519616A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a fiber-reinforced polylactic acid compound and a preparation method thereof. The compound is prepared from raw materials in parts by weight as follows: 20-45 parts of poly DL-lactide, 30-65 parts of poly L-lactic acid, 10-20 parts of bamboo fibers, 2-8 parts of chitosan fibers and 1-5 parts of polyimide fibers. Tensile strength of the compound can reach 90 MPa, and bending strength can reach 190 MPa. The compound can be processed to form absorbable devices for various orthopedic surgeries, good biocompatibility and absorbability of polylactic acid are kept, and material strength is remarkably improved.
Description
Technical field
The present invention relates to a kind of manufacture can absorb the biomaterial of medical device, more particularly, it relates to poly-
Lactate material it is modified, using fiber reinforcement poly-lactic acid material so as to which mechanical strength increases.
Background technology
Poly-lactic acid material has good biocompatibility, can be fully absorbed by human body, nontoxic, have no side effect, at present, profit
The devices such as plate in orthopaedics, screw, internal fixation bar are processed into poly-lactic acid material, gradually replace metal device, make patient without
Second operation is needed, mitigates the pain and burden of patient.But, the intensity of this kind of material is high not enough, it is impossible to used as special height
The needs of strength materials.
Fiber reinforcement can significantly improve the intensity of macromolecular material, be industrially widely applied, in biological material
Material field, also has started to using fiber reinforcement technology come the intensity of reinforcing material, such as：Document report (Int.J.Oral
Maxillofac.Surg.1993.22：51～57) using polyglycolic acid (PGA) fiber and calcium metaphosphate silk fiber strengthening material
The intensity of material.CN1362447A discloses a kind of fibre-reinforced polylactic acid composition, including：In terms of parts by weight：PLA
60 parts～95 parts, 5 parts～40 parts degradable of fiber；Wherein, degradable fiber is fine selected from chitin fiber, glutin
Dimension, modified human hair keratin fiber, modified cellulose or polyimide fiber.However, due to own material low intensity, it is enhanced
Effect is not high.
The content of the invention
It is an object of the invention to provide a kind of fibre-reinforced polylactic acid composition and preparation method thereof, this material can plus
Absorbable device of the work into various bone surgeries, that is, maintain the biocompatibility well and absorbability of PLA, its
The strength of materials increases significantly.
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
PDLLA 20-45 parts, such as 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts or 42 parts etc.；
Poly (l-lactic acid) 30-65 parts, such as 32 parts, 35 parts, 38 parts, 40 parts, 45 parts, 50 parts, 55 parts, 58 parts or 62 parts etc.；
Bamboo fibre 10-30 parts, such as 12 parts, 15 parts, 18 parts or 19 parts etc..
Chitin fiber 2-8 parts, such as 3 parts, 4,5 parts, 6 parts, 7 parts or 7.5 parts etc.；
Polyimide fiber 1-5 parts, such as 2 parts, 3 parts, 4 parts or 4.5 parts etc..
The present invention strengthens answering for PDLLA and poly (l-lactic acid) using bamboo fibre, chitin fiber and polyimide fiber
Compound, up to 90MPa, bending strength is up to 190MPa for the tensile strength of the compound for obtaining.
Used as preferred technical scheme, the compound is prepared by the following raw material by weight：
Used as preferred technical scheme, the compound is prepared by the following raw material by weight：
Used as preferred technical scheme, the compound is prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 500,000-80 ten thousand, such as 52-62 ten thousand, 58-78 ten thousand, 60-79 ten thousand or 65-75
Ten thousand etc..
The weight average molecular weight of the poly (l-lactic acid) is 30,000-10 ten thousand, such as 3.1-9.2 ten thousand, 3.5-8 ten thousand, 4-7 ten thousand, 3-6 ten thousand, 5-
90000 or 6-9.5 ten thousand etc..
The length of the chitin fiber be 20-50mm, such as 22mm, 25mm, 28mm, 30mm, 32mm, 35mm, 40mm,
45mm or 48mm etc., such as a diameter of 0.5-1mm, 0.6mm, 0.7mm, 0.8mm or 0.9mm etc..
4～the 5cN/dtex of intensity of the polyimide fiber, such as 4.5cN/dtex etc., elongation 5%～7%, such as
6%, 10～12GPa of modulus, such as 11GPa etc..
The length of the bamboo fibre is 10-20mm, such as 12mm, 13mm, 14mm, 15mm, 16mm, 17mm or 19mm etc., directly
Footpath is 0.1-0.5mm, such as 0.2mm, 0.3mm, 0.4mm etc..
An object of the present invention is also resided in and provides a kind of preparation method of compound as above, the preparation method
For：
Each raw material of formula ratio is kneaded on kneading machine uniformly, processing temperature 160-185 DEG C, such as 162 DEG C, 165 DEG C,
It is 168 DEG C, 170 DEG C, 172 DEG C, 175 DEG C or 180 DEG C etc., then, hot-forming on vulcanizing press, make described being combined
Thing.
The reinforcing fiber adopted in the present invention must be degradable fiber, and be compatible with poly-lactic acid material.
The present invention is compound using bamboo fibre, polyimide fiber, chitin fiber enhancing PDLLA and poly (l-lactic acid)
Thing, up to 90MPa, bending strength is up to 190MPa for the tensile strength of the compound for obtaining.
Using fibre-reinforced polylactic acid composition, the absorbable device of various bone surgeries can be processed into, such as plate,
Screw, internal fixation bar etc..It is when illustrating the processing for high-strength plate, first that fiber is arranged in parallel in certain direction, then will
Pour into a mould after PLA melting, be pressed into sheet material.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 500,000-60 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 30,000-5 ten thousand.
The length of the chitin fiber is 20-30mm, a diameter of 0.5-0.6mm.
Intensity 4cN/dtex of the polyimide fiber, elongation 5%, modulus 10GPa.
The length of the bamboo fibre is 10-12mm, a diameter of 0.1-0.3mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
It is 165 DEG C, then, hot-forming on vulcanizing press, make compound.
Embodiment 2
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 700,000-80 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 60,000-10 ten thousand.
The length of the chitin fiber is 30-50mm, a diameter of 0.8-1mm.
Intensity 4cN/dtex of the polyimide fiber, elongation 7%, modulus 12GPa.
The length of the bamboo fibre is 12-20mm, a diameter of 0.3-0.5mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
It is 170 DEG C, then, hot-forming on vulcanizing press, make compound.
Embodiment 3
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 700,000-80 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 80,000-10 ten thousand.
The length of the chitin fiber is 20-30mm, a diameter of 0.5-0.7mm.
Intensity 4.5cN/dtex of the polyimide fiber, elongation 6%, modulus 11GPa.
The length of the bamboo fibre is 15-20mm, a diameter of 0.1-0.3mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
It is 170 DEG C, then, hot-forming on vulcanizing press, make compound.
Embodiment 4
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 700,000-80 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 80,000-10 ten thousand.
The length of the chitin fiber is 20-30mm, a diameter of 0.5-0.7mm.
Intensity 4.5cN/dtex of the polyimide fiber, elongation 6%, modulus 11GPa.
The length of the bamboo fibre is 15-20mm, a diameter of 0.1-0.3mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
It is 185 DEG C, hot-forming on vulcanizing press, make compound.
Embodiment 5
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 700,000-80 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 80,000-10 ten thousand.
The length of the chitin fiber is 20-30mm, a diameter of 0.5-0.7mm.
Intensity 4.5cN/dtex of the polyimide fiber, elongation 6%, modulus 11GPa.
The length of the bamboo fibre is 15-20mm, a diameter of 0.1-0.3mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
172 DEG C, make compound.
Embodiment 6
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The weight average molecular weight of the PDLLA is 700,000-80 ten thousand.
The weight average molecular weight of the poly (l-lactic acid) is 80,000-10 ten thousand.
The length of the chitin fiber is 20-30mm, a diameter of 0.5-0.7mm.
Intensity 4.5cN/dtex of the polyimide fiber, elongation 6%, modulus 11GPa.
The length of the bamboo fibre is 15-20mm, a diameter of 0.1-0.3mm.
Its preparation method is：Each raw material of formula ratio is kneaded uniformly under high-rate of shear on kneading machine, processing temperature
165 DEG C, make compound.
Comparative example 1
A kind of fibre-reinforced polylactic acid composition, its raw material composition except PDLLA is replaced with addition to poly (l-lactic acid), its
It is remaining same as Example 6.
Comparative example 2
A kind of fibre-reinforced polylactic acid composition, its raw material composition except poly (l-lactic acid) is replaced with addition to PDLLA, its
It is remaining same as Example 6.
Comparative example 3
A kind of fibre-reinforced polylactic acid composition, its raw material are constituted in addition to bamboo fibre is not contained, remaining and 6 phase of embodiment
Together.
Comparative example 4
A kind of fibre-reinforced polylactic acid composition, its raw material are constituted in addition to chitin fiber is not contained, remaining and enforcement
Example 6 is identical.
Comparative example 5
A kind of fibre-reinforced polylactic acid composition, its raw material are constituted in addition to polyimide fiber is not contained, remaining and reality
Apply example 6 identical.
Comparative example 6
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The preparation method of the fiber reinforcement polylactic acid composition is identical with the preparation method described in embodiment 6.
Comparative example 7
A kind of fibre-reinforced polylactic acid composition, the compound are prepared by the following raw material by weight：
The preparation method of the fiber reinforcement polylactic acid composition is identical with the preparation method described in embodiment 6.
About the fibre-reinforced poly-lactic acid material performance measurement described in embodiment 1-6 and comparative example 1-7 as shown in table 1,
And compare with common PLA.
Stretching strength determination：By hot-forming, sample shape is mute tinkling of pieces of jade shape to test sample, 23 DEG C of test temperature, humidity
60%, rate of extension is 2mm/min.
Bending strength is determined：Test sample is by hot-forming, its length ＞ 55mm, a diameter of 4.5mm, test temperature 23
DEG C, humidity 60%, loading pressure head radius are 5.0mm.
1 fibre-reinforced poly-lactic acid material mechanical property of table
Shown by the above results, compared with common lactate material, its machinery is strong for the fiber reinforcement poly-lactic acid material of the present invention
Degree increases significantly, and extends the purposes of material, is expected to be used for tubulose cortex Fracture internal fixaiion, such as internal fixation screw plate system
Deng.
The compound of the present invention is processed into Fracture internal fixaiion device, has good biocompatibility, energy with tissue
Fully absorbed by human body, it is nontoxic, have no side effect.Clinical effectiveness shows：After implantation human body, intensity is kept for 12～30 weeks, 18 months
Left and right fully absorbs.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a kind of fibre-reinforced polylactic acid composition, it is characterised in that the compound is by weight by the following raw material system
It is standby to obtain：
2. compound according to claim 1, it is characterised in that the compound is prepared by the following raw material by weight
Obtain：
3. compound according to claim 1 and 2, it is characterised in that the compound is by weight by the following raw material
Prepare：
4. compound according to claim 3, it is characterised in that the compound is prepared by the following raw material by weight
Obtain：
5. the compound according to one of claim 1-4, it is characterised in that the weight average molecular weight of the PDLLA is
500000-80 ten thousand.
6. the compound according to one of claim 1-5, it is characterised in that the weight average molecular weight of the poly (l-lactic acid) is 3
Ten thousand -10 ten thousand.
7. the compound according to one of claim 1-6, it is characterised in that the length of the chitin fiber is 20-
50mm, a diameter of 0.5-1mm.
8. the compound according to one of claim 1-7, it is characterised in that the intensity 4 of the polyimide fiber～
5cN/dtex, elongation 5%～7%, 10～12GPa of modulus.
9. the compound according to one of claim 1-8, it is characterised in that the length of the bamboo fibre is 10-20mm, directly
Footpath is 0.1-0.5mm.
10. the preparation method of the compound according to one of claim 1-9, it is characterised in that the preparation method is：
Each raw material of formula ratio is kneaded on kneading machine uniformly, processing temperature 160-185 DEG C, then, on vulcanizing press
It is hot-forming, make described compound.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611015129.5A CN106519616A (en) | 2016-11-18 | 2016-11-18 | Fiber-reinforced polylactic acid compound and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611015129.5A CN106519616A (en) | 2016-11-18 | 2016-11-18 | Fiber-reinforced polylactic acid compound and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189516A (en) * | 1997-01-30 | 1998-08-05 | 南京大学 | Thermoplasticity macromolecule composite, its preparing method and applications |
| CN1362447A (en) * | 2001-01-05 | 2002-08-07 | 成都迪康中科生物医学材料有限公司 | Fiber reinforced polylactic acid composition |
| CN1537892A (en) * | 2003-04-18 | 2004-10-20 | 四川迪康科技药业股份有限公司 | Fiber reinforced poly lactic acid material and use |
| CN101955638A (en) * | 2010-09-21 | 2011-01-26 | 浙江大学宁波理工学院 | Plant fiber-reinforced polylactic acid foam material and preparation method thereof |
| CN106075601A (en) * | 2016-07-05 | 2016-11-09 | 湖南师范大学 | A kind of bamboo fibre/degradable multiporous material of hydroxyapatite/polylactic acid class tri compound and preparation method thereof |
-
2016
- 2016-11-18 CN CN201611015129.5A patent/CN106519616A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189516A (en) * | 1997-01-30 | 1998-08-05 | 南京大学 | Thermoplasticity macromolecule composite, its preparing method and applications |
| CN1362447A (en) * | 2001-01-05 | 2002-08-07 | 成都迪康中科生物医学材料有限公司 | Fiber reinforced polylactic acid composition |
| CN1537892A (en) * | 2003-04-18 | 2004-10-20 | 四川迪康科技药业股份有限公司 | Fiber reinforced poly lactic acid material and use |
| CN101955638A (en) * | 2010-09-21 | 2011-01-26 | 浙江大学宁波理工学院 | Plant fiber-reinforced polylactic acid foam material and preparation method thereof |
| CN106075601A (en) * | 2016-07-05 | 2016-11-09 | 湖南师范大学 | A kind of bamboo fibre/degradable multiporous material of hydroxyapatite/polylactic acid class tri compound and preparation method thereof |
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