CN105368022B - A kind of preparation method of polycaprolactone self-reinforced material - Google Patents
A kind of preparation method of polycaprolactone self-reinforced material Download PDFInfo
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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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/30—Applications used for thermoforming
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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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to a kind of preparation method of polycaprolactone self-reinforced material, the preparation method of polycaprolactone self-reinforced material, including：Polycaprolactone section is carried out into melt spinning, as-spun fibre is obtained, is drawn high, obtain polycaprolactone and draw high fiber；By dry polycaprolactone diols and diisocyanate under nitrogen protective condition, 60 DEG C of 30 40min of reaction then heat to 80 DEG C of reaction 3h, obtain isocyanate-terminated polycaprolactone prepolymers body；By above-mentioned isocyanate-terminated polycaprolactone prepolymers body and two kinds of different molecular weight polycaprolactone diols reactions, reaction temperature is 180 DEG C, and the time is 10 20min, obtains low melting point polycaprolactone；Polycaprolactone is drawn high into fiber through after low melting point polycaprolactone solution, hot blast drying, hot pressing, cooling are obtained final product.The inventive method is simple, and raw material is easy to get, and has broad application prospects in tissue engineering bracket field.
Description
Technical field
The invention belongs to the preparation field of polycaprolactone material, more particularly to a kind of preparation of polycaprolactone self-reinforced material
Method.
Background technology
As the good aliphatic polyester of a kind of fully biodegradable and biocompatibility, polycaprolactone (PCL) quilt
It is considered a kind of good organizational project substitution material.Tissue engineering bracket needs breeding growth and the mechanics for meeting cell simultaneously
Performance two is big to be required.Polycaprolactone tissue engineering bracket prepared by the technologies such as precinct laser sintering, fused glass pellet, 3D printing
Although gathering so as to be conducive to breeding and growth of the cell on support with the structure more similar with natural extracellular matrix
The mechanical property of caprolactone tissue engineering bracket is poor to be difficult to directly application.As polycaprolactone is a kind of flexible point in itself
Subchain, rigidity are poor, it is difficult to be applied to cartilage tissue engineered and bone tissue engineer field directly as load-bearing material.Therefore
The enhanced method of research and utilization polymeric material is lifted its mechanical strength, so as to be applied to organizational project neck as load-bearing material
Domain.
At present, many researcheres are prepared for polycaprolactone reinforcing material, such as Weihua by the method for blending or copolymerization
Polycaprolactone/reduction-oxidation graphite composite material prepared by Kai et al., by polycaprolactone is carried out with redox graphene
Solvent is blended, and controls the mass ratio of polycaprolactone and redox graphene, obtains the polycaprolactone/reduction of different quality containing
Stannic oxide/graphene nano composite.Compared with polycaprolactone, the Young's moduluss of composite are brought up to from 258.1Mpa
337.7Mpa。[Bingjie Wang,Yiguo Li,Gengsheng Weng,Zhiqiang Jiang,Peng Chen,
Zongbao Wang*,Qun Gu*.Reduced graphene oxide enhances the crystallization and
orientation of poly(ε-caprolactone).Composites Science and Technology,2014,
96,63-70].Although this kind of method effectively raises the mechanical strength of polycaprolactone, but due to the doping of nanoparticle,
So that the biocompatibility of composite has suffered a certain degree of destruction, cytoactive have dropped 50% in 24h.In addition,
As the cylinder accumulation that redox graphene nanoparticle does not have biological degradability, nanoparticle is also brought for its application
It is difficult.Zhou Ziyan et al. improves the mechanical strength of polycaprolactone using the method for the modified polycaprolactone of chitosan graft.[week is purple
Swallow, Peng Guifang, Huang enter chitosan graft polycaprolactone and national macromolecule in 2007 are acted on to the synchronous activeness and quietness of polycaprolactone
Scientific paper public lecture].But the hemostasis effect of shitosan makes its blood compatibility very poor, many researchs at present are focused on finding
Solution to this problem, improves its blood compatibility, extends its application on bioengineered tissue so as to more
Safely and effectively with human contact.Therefore the tissue engineering bracket material for being prepared from self-reinforcing polycaprolactone causes people pole
Big interest.
Zhang JM et al. from " skin-core " structure bicomponent fibre, skin be low-melting point PET copolymer, fusing point
For 210 DEG C, core is high-melting-point PET copolymer, and fusing point is 250 DEG C.Bicomponent fibre is wound on mould and then by hot pressing
Technology melts " skin " so as to " core " is coupled together preparation PET self-reinforced composite materials, and, used as base phase, core is used as enhancing for skin
Phase, the stretch moduluses for measuring enhancing composite are 10.4Gpa, and compared with former PET, stretch moduluses improve nearly 286%.
[Zhang JM,Pejis T*.Self-reinforced poly(ethylene terephthalate)composites by
hot consolidation of Bi-component PET yarns[J].Composites Part A:Applied
science and Manufacturing.2010,41,964-972]；
These technologies for preparing reinforcing material provide the foundation to prepare polycaprolactone self-reinforced material, and polycaprolactone is from increasing
Tissue engineering bracket prepared by strong material has broad prospects.
The content of the invention
The technical problem to be solved is to provide a kind of preparation method of polycaprolactone self-reinforced material, the preparation
Method is simple to operate, and reaction raw materials are easy to get, with low cost, while not destroying the biocompatibility and biological drop of polycaprolactone itself
Xie Xing, has huge application prospect in tissue engineering bracket field.
A kind of preparation method of the polycaprolactone self-reinforced material of the present invention, including：
(1) polycaprolactone section is carried out into melt spinning, obtains as-spun fibre, then as-spun fibre is drawn high, obtain
Fiber is drawn high to polycaprolactone；
(2) by dry polycaprolactone diols and diisocyanate under nitrogen protective condition, 60 DEG C of reaction 30-
40min, then heats to 80 DEG C of reaction 3h, obtains isocyanate-terminated polycaprolactone prepolymers body；Wherein polycaprolactone two
First alcohol is 1 with the mol ratio of diisocyanate:1.8-1:2.0；
(3) by above-mentioned isocyanate-terminated polycaprolactone prepolymers body and two kinds of different molecular weight polycaprolactone diolss
Reaction, reaction temperature are 180 DEG C, and the time is 10-20min, obtains low melting point polycaprolactone；
(4) polycaprolactone is drawn high into fiber through after low melting point polycaprolactone solution, hot blast drying obtains " skin-core " knot
Structure fiber, then winds around, cooling, obtains final product polycaprolactone self-reinforced material.
Polycaprolactone section in the step (1) is cut into slices for commercialization polycaprolactone.
In the step (1) polycaprolactone section number-average molecular weight be Mn=70000g/mol-80000g/mol, many points
Scattered sex index PDI=1.1-1.3.
In the step (1), the temperature of melt spinning is 140-160 DEG C, and spinning speed is 40-60m/min；Stretching is concrete
Condition is：Draft temperature is room temperature, and stretching ratio is 3-10 times.
In the step (2), polycaprolactone diols is low-molecular-weight polycaprolactone diols, and molecular weight is Mn=
1000g/mol-2000g/mol。
In the step (2), diisocyanate is hexamethylene diisocyanate.
In the step (3), the molecular weight of two kinds of different molecular weight polycaprolactone diolss is respectively：Mn=1000g/
mol-2000g/mol、Mn=2000g/mol-2500g/mol.
Isocyanate-terminated polycaprolactone prepolymers body, M in step (3)n=1000g/mol-2000g/mol's gathers oneself
Lactone dihydroxylic alcohols, MnThe mass ratio of the polycaprolactone diols of=2000g/mol-2500g/mol is 1-3g, 14-17g, 10-
14g。
In the step (3), the melting range of low melting point polycaprolactone is 48-54 DEG C.
In the step (4), the solvent of low melting point polycaprolactone solution is：In chloroform, acetone, dimethylformamide
One or more；The mass percentage concentration of low melting point polycaprolactone solution is 10-20%.
It is 0.3-1.0m/ that in the step (4), polycaprolactone draws high fiber through the speed of low melting point polycaprolactone solution
mim；Hot pressing parameterses are：Temperature is 48-55 DEG C, and hot pressing pressure is 2.9-5.0KN, and hot pressing time is 15-30min.
Polycaprolactone as-spun fibre is prepared initially with melt spinning technology in the present invention, and as-spun fibre is stretched
Obtain polycaprolactone stretching fiber.Low melting point polycaprolactone is prepared using the method for melt polymerization；Polycaprolactone is stretched into fiber
Through after the solution of low melting point polycaprolactone, hot blast drying is had the bicomponent fibre of " skin-core " structure, is utilized " skin-core "
Bicomponent fibre is carried out hot pressing under cortex melting temperature by the difference of fusing point, makes " skin " of fusing that " core " is bondd, from
And remain the mechanical property of core fibers, obtain with complete biocompatibility, totally biodegradable polycaprolactone from
Strengthen composite.
Beneficial effect
(1) preparation method of the invention is simple to operate, and reaction raw materials are easy to get, with low cost, while not destroying polycaprolactone
The biocompatibility and biological degradability of itself, has huge application prospect in tissue engineering bracket field；
(2) the polycaprolactone self-reinforced composite material Young's moduluss that the present invention is prepared are 230.26-279.34Mpa,
Fracture strength is 40.22-62.47Mpa, and elongation at break is 44.20%-36.00%, and former polycaprolactone Young's moduluss are
175.24Mpa, fracture strength are 17.83Mpa, and elongation at break is 710.00%.
Description of the drawings
Fig. 1 stretches the feature DSC collection of illustrative plates of fiber (λ=6) for the low melting point polycaprolactone in embodiment 3 and polycaprolactone；
Fig. 2 is the feature SEM figure of the polycaprolactone self-reinforced composite material that embodiment 3 is obtained；
Feature stress strain curve collection of illustrative plates of the Fig. 3 for the polycaprolactone self-reinforced composite material of embodiment 2-4, wherein illustration correspondence
In stress strain curve, range of strain draws high curve for 0%-80% parts.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) preparation of low melting point polycaprolactone co-polymer
Take the polycaprolactone diols (M of 20g dryingsn=1000g/mol) in 100ml there-necked flasks, add 6.4ml six
Methylene diisocyanate, the lower 60 DEG C of reactions 30min of nitrogen protective condition then heat to 80 DEG C of reaction 3h and obtain isocyanates
The polycaprolactone prepolymers body of end-blocking is standby；Afterwards by 1.61g polycaprolactone diols (Mn=1000g/mol), 15g polycaprolactones
Dihydroxylic alcohols (Mn=2000g/mol), 13.39g polycaprolactone prepolymers bodies are placed in 100ml there-necked flasks, are reacted in 180 DEG C
20min is obtained low melting point polycaprolactone, and onset melting temperature is 46.0 DEG C, and melting final temperature is 55.2 DEG C.
(2) preparation of polycaprolactone self-reinforced composite material
By polycaprolactone section (Mn=70000g/mol-80000g/mol, PDI=1.1-1.3) carry out melt spinning system
Polycaprolactone as-spun fibre is obtained, spinning temperature is 160 DEG C, and spinning speed is 40m/min；By as-spun fibre according to draw ratio be 3
Multistage stretching is carried out, draft temperature is that room temperature is obtained polycaprolactone stretching fiber；Polycaprolactone is stretched into fiber with 1m/min's
Speed is obtained skin-core structure fiber through the low melting point polycaprolactone solution that mass fraction is 15%, hot-air seasoning；Core-skin is tied
Structure fiber is wrapped on hot pressing die, 52.5 DEG C of hot pressing temperature, hot pressing time 15min, hot pressing pressure 2.94KN, after hot pressing terminates
Naturally cool to room temperature and be obtained polycaprolactone self-reinforced composite material, its Young's modulus is 215.75Mpa, fracture strength
26.70Mpa, elongation at break 43.50%.
Embodiment 2
With the low melting point polycaprolactone in embodiment one as raw material, polycaprolactone self-reinforced composite material is prepared.
By polycaprolactone section (Mn=70000g/mol-80000g/mol, PDI=1.1-1.3) carry out melt spinning system
Polycaprolactone as-spun fibre is obtained, spinning temperature is 160 DEG C, and spinning speed is 40m/min；By as-spun fibre according to draw ratio be 4
Multistage stretching is carried out, draft temperature is that room temperature is obtained polycaprolactone stretching fiber；Polycaprolactone is stretched into fiber with 1m/min's
Speed is obtained skin-core structure fiber through the low melting point polycaprolactone solution that mass fraction is 15%, hot-air seasoning；Core-skin is tied
Structure fiber is wrapped on hot pressing die, 52.5 DEG C of hot pressing temperature, hot pressing time 15min, hot pressing pressure 3.92KN, after hot pressing terminates
Naturally cool to room temperature and be obtained polycaprolactone self-reinforced composite material, its Young's modulus is 252.38Mpa, fracture strength
55.78Mpa, elongation at break 40.53%.
Embodiment 3
With the low melting point polycaprolactone in embodiment one as raw material, polycaprolactone self-reinforced composite material is prepared
By polycaprolactone section (Mn=70000g/mol-80000g/mol, PDI=1.1-1.3) carry out melt spinning system
Polycaprolactone as-spun fibre is obtained, spinning temperature is 160 DEG C, and spinning speed is 40m/min；By as-spun fibre according to draw ratio be 6
Multistage stretching is carried out, draft temperature is that room temperature is obtained polycaprolactone stretching fiber；Polycaprolactone is stretched into fiber with 1m/min's
Speed is obtained skin-core structure fiber through the low melting point polycaprolactone solution that mass fraction is 15%, hot-air seasoning；Core-skin is tied
Structure fiber is wrapped on hot pressing die, 52.5 DEG C of hot pressing temperature, hot pressing time 15min, hot pressing pressure 3.92KN, after hot pressing terminates
Naturally cool to room temperature and be obtained polycaprolactone self-reinforced composite material, its Young's modulus is 279.34Mpa, fracture strength
62.47Mpa, elongation at break 36.00%.
Embodiment 4
With the low melting point polycaprolactone in embodiment one as raw material, polycaprolactone self-reinforced composite material is prepared
By polycaprolactone section (Mn=70000g/mol-80000g/mol, PDI=1.1-1.3) carry out melt spinning system
Polycaprolactone as-spun fibre is obtained, spinning temperature is 160 DEG C, and spinning speed is 40m/min；By as-spun fibre according to draw ratio be 3
Multistage stretching is carried out, draft temperature is that room temperature is obtained polycaprolactone stretching fiber；Polycaprolactone is stretched into fiber with 1m/min's
Speed is obtained skin-core structure fiber through the low melting point polycaprolactone solution that mass fraction is 15%, hot-air seasoning；Core-skin is tied
Structure fiber is wrapped on hot pressing die, 52.5 DEG C of hot pressing temperature, hot pressing time 15min, hot pressing pressure 3.92KN, after hot pressing terminates
Naturally cool to room temperature and be obtained polycaprolactone self-reinforced composite material, its Young's modulus is 230.52Mpa, fracture strength
41.28Mpa, elongation at break 39.85%.
Claims (8)
1. a kind of preparation method of polycaprolactone self-reinforced material, including：
(1) polycaprolactone section is carried out into melt spinning, obtains as-spun fibre, then as-spun fibre is stretched, gathered
Caprolactone stretches fiber；
(2) by dry polycaprolactone diols and diisocyanate under nitrogen protective condition, 60 DEG C of reaction 30-40min, so
After be warming up to 80 DEG C reaction 3h, obtain isocyanate-terminated polycaprolactone prepolymers body；Wherein polycaprolactone diols and two
The mol ratio of isocyanates is 1:1.8-1:2.0；Wherein in step (2), polycaprolactone diols is low-molecular-weight polycaprolactone two
First alcohol, molecular weight are Mn=1000g/mol-2000g/mol；
(3) will be above-mentioned isocyanate-terminated polycaprolactone prepolymers body anti-with two kinds of different molecular weight polycaprolactone diolss
Should, reaction temperature is 180 DEG C, and the time is 10-20min, obtains low melting point polycaprolactone；Two kinds of differences point wherein in step (3)
The molecular weight of son amount polycaprolactone diols is respectively：Mn=1000g/mol-2000g/mol, Mn=2000g/mol-2500g/
mol；
(4) by polycaprolactone stretching fiber through after low melting point polycaprolactone solution, hot blast drying, hot pressing, cooling, obtain final product it is poly- oneself
Lactone self-reinforced material.
2. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(1) in, the number-average molecular weight of polycaprolactone section is Mn=70000g/mol-80000g/mol, polydispersity index PDI=
1.1-1.3。
3. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(1) in, the temperature of melt spinning is 140-160 DEG C, and spinning speed is 40-60m/min；Stretching is specially：Draft temperature is room
Temperature, stretching ratio are 3-10 times.
4. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(2) in, diisocyanate is hexamethylene diisocyanate.
5. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：Step (3)
In isocyanate-terminated polycaprolactone prepolymers body, MnThe polycaprolactone diols of=1000g/mol-2000g/mol, Mn=
The mass ratio of the polycaprolactone diols of 2000g/mol-2500g/mol is 1-3g:14-17g:10-14g.
6. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(3) in, the melting range of low melting point polycaprolactone is 48-54 DEG C.
7. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(4) in, the solvent of low melting point polycaprolactone solution is：One or more in chloroform, acetone, dimethylformamide；Eutectic
The mass percentage concentration of point polycaprolactone solution is 10-20%.
8. the preparation method of a kind of polycaprolactone self-reinforced material according to claim 1, it is characterised in that：The step
(4) in, polycaprolactone stretching fiber is 0.3-1.0m/min through the speed of low melting point polycaprolactone solution；Hot pressing parameterses
For：Temperature is 48-55 DEG C, and hot pressing pressure is 2.9-5.0KN, and hot pressing time is 15-30min.
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