CN106380804A - Preparation method of high-performance polycaprolactone/polylactic acid blend material - Google Patents
Preparation method of high-performance polycaprolactone/polylactic acid blend material Download PDFInfo
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- CN106380804A CN106380804A CN201610827769.XA CN201610827769A CN106380804A CN 106380804 A CN106380804 A CN 106380804A CN 201610827769 A CN201610827769 A CN 201610827769A CN 106380804 A CN106380804 A CN 106380804A
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- polycaprolactone
- polylactic acid
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic 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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a high-performance polycaprolactone/polylactic acid blend material, relating to a preparation technique of a polycaprolactone/polylactic acid blend. The method comprises the following steps: putting polycaprolactone and polylactic acid into a Banbury mixer, and carrying out melt blending at 170 DEG C to obtain a polycaprolactone/polylactic acid blend; heating the polycaprolactone/polylactic acid blend to 175 DEG C, treating under the pressure of 10-15 MPa, and annealing by cooling; and finally, cooling to room temperature to obtain the high-performance polycaprolactone/polylactic acid blend material. An annealing technique is utilized to control the supramolecular shape in the polycaprolactone and the interface compatibility of the polycaprolactone; the annealed polylactic acid has more obvious heterogeneous nucleation actions on the polycaprolactone, so the compatibility between the two phases is obviously enhanced before annealing; and thus, the mechanical properties of the polycaprolactone/polylactic acid blend material are greatly enhanced.
Description
Technical field
The present invention relates to the technology of preparing of the blend of polycaprolactone and polylactic acid, particularly polycaprolactone degree of crystallinity and
The control technique field of polycaprolactone/polylactic acid blend material performance.
Background technology
With the requirement of environmental conservation and economic development, biodegradable macromolecule such as polycaprolactone, polylactic acid etc. are made
Of increasing concern for new degradable high polymer material.They have good thermoplasticity, biocompatibility, biology can drop
Solution property and tissue absorbability, therefore not only in general-purpose plastics field, as drug controlled release base in terms of biomedical engineering
Material, the tissue engineering bracket of porous, the aspect such as packaging also has potential using value.
Single polycaprolactone or polylactic acid have respective shortcoming in performance, such as the glass transition temperature of polylactic acid
For -60 DEG C, it is in rubbery state under room temperature, shows as excellent toughness, elongation at break is high, but its tensile strength is low.And it is poly- newborn
Acid then has degradation rate and preferable tensile strength faster, but the poor easily flexural deformation of toughness.Therefore in order to utilize it
Performance complement, polycaprolactone and polylactic acid melt blending are the effective ways improving their modulus and intensity.
Between polycaprolactone and polylactic acid, the thermodynamic (al) incompatible intermingling material phase domain making them is larger and interface is glued
Knot is loose, and performance is unable to reach the expected situation envisioned and combination property with straight polymer compared with decline possibly even occurs, institute
To have to co-mixing system is modified.And polycaprolactone and polylactic acid are all typical half crystal formation polymer, their thing
Rationality can be strongly depend on the supermolecule form of material internal, i.e. crystallization degree and crystalline texture.Therefore to polycaprolactone and poly-
For lactic acid blend, its crystallization behavior has important impact to the mechanical property of material, degradation behavior etc..
Content of the invention
Present invention aim at proposing a kind of preparation side of highly crystalline, high performance polycaprolactone/polylactic acid blend material
Method.
The present invention first polycaprolactone and polylactic acid is placed in banbury, under 170 DEG C of temperature conditionss, melt blending, and take
Obtain the blend of polycaprolactone and polylactic acid, then the blend of polycaprolactone and polylactic acid is warming up to 175 DEG C, in pressure 10-
After processing under conditions of 15MPa, it is cooled to 100～145 DEG C of annealing 3～12h, is finally cooled to room temperature, obtain final product high performance poly-
Caprolactone/polylactic acid blend material.
The polycaprolactone of the present invention is 40,000～60,000 for number-average molecular weight, and fusing point is that 50～70 DEG C of biology can drop
Solution and biocompatible macromolecule polyester.Polylactic acid is 80,000～120,000 for number-average molecular weight, and fusing point is 150～180 DEG C
Biodegradable polymer material.Polycaprolactone and polylactic acid are that thermodynamics are incompatible, the cold crystallization temperature scope of polylactic acid
For 100～145 DEG C, and their mass ratio is 80/20～50/50.The fusing point of polycaprolactone and glass transition temperature are far low
In polylactic acid, and they are all hemihedral crystal polymer, and its physical property is strongly depend on the supermolecule form of material internal.
Inventor finds through research：Once hemihedral crystal polymeric material self performance such as crystal property improves, material
Good performance can be shown.The crystallization of polylactic acid depends not only upon its volume ratio, is also strongly depend on its annealing process.
The present invention designs to control its supermolecule form in polycaprolactone and the interface phase with polycaprolactone using annealing process
Before capacitive, after finding polylactic acid annealing, becomes apparent to the heterogeneous nucleating effect of polycaprolactone, and the biphase compatibility is than annealing
Significantly improve, therefore after polylactic acid annealing cold crystallization, the mechanical property of polycaprolactone/polylactic acid blend material has very big proposing
Rise.
Further, the mixing quality of polycaprolactone of the present invention and polylactic acid is than for 1～4: 1.In such ratio
Under, polycaprolactone is matrix continuous phase, and polylactic acid is dispersion phase, and change under the annealing conditions of technique initialization is that dispersion is met
The degree of crystallinity of lactic acid and supermolecule form, polycaprolactone itself is unaffected, the degree of crystallinity of dispersion phase polylactic acid and supermolecule shape
The change of state improves the biphase compatibility, thus finally improving the mechanical property of the intermingling material with polycaprolactone as matrix.
Brief description
Fig. 1 is embodiment 1 and comparative example 1, the 2 DSC exotherm when 5k/min lowers the temperature.
Fig. 2 is load-deformation curve in drawing process for the material that obtains of embodiment 1 and comparative example 1,2.
Specific embodiment
Below in conjunction with the accompanying drawings and preferred forms the invention will be further described so that the public to invention in have
Overall and sufficient understanding, and not limiting the scope of the present invention.Preceding sections have fully disclosed the present invention can
With the protection domain implemented, therefore all equivalents known to any field carrying out according to the disclosure of invention, belong to
Infringement to the present invention.
Other advantages of the present invention and effect by following specific embodiment continuing on.
In following example, polycaprolactone is number-average molecular weight about 40,000～60,000, and melt index is about 7g/10min
(160 DEG C/2.16kg), melt temperature is 50～70 DEG C of biodegradable and biocompatible polymer copolymerization ester；Polylactic acid
For number-average molecular weight about 80,000～120,000, melt index about 8g/10min (190 DEG C/2.16kg), melt temperature 150
～180 DEG C of Biodegradable high-molecular polyester.The Newtonian shear viscosity of polycaprolactone and polylactic acid is than for 1/16.
First, embodiment 1
1st, dried polycaprolactone/polylactic acid ratio is placed in Haake torque rheometer in 170 DEG C of temperature, rotor speed
Melt blending 6min under 50 r/min, the blend of prepared polycaprolactone/polylactic acid.
When mixed above, polycaprolactone and the mass ratio that feeds intake of polylactic acid are 70/30.
2nd, by the blend being obtained in 175 DEG C, it is molded 6 min under 14MPa, then temperature is dropped to 100～145 DEG C of annealing
3～12h, finally drops to room temperature again, obtains the blend of highly crystalline polycaprolactone/polylactic acid.
2nd, comparative example 1
1st, dried polycaprolactone is placed in 80 DEG C of temperature in Haake torque rheometer, molten under rotor speed 50 r/min
Melt blending 6min, prepared polycaprolactone pure material.
2nd, by the polycaprolactone pure material being obtained in 80 DEG C, it is molded 6 min under 14MPa, then temperature is dropped to room temperature.
3rd, comparative example 2
1st, dried polycaprolactone/polylactic acid ratio is placed in Haake torque rheometer in 170 DEG C of temperature, rotor speed
Melt blending 6min under 50 r/min, the blend of prepared polycaprolactone/polylactic acid.
When mixed above, polycaprolactone and the mass ratio that feeds intake of polylactic acid are 70/30.
2nd, by the polycaprolactone/polylactic acid blend being obtained in 175 DEG C, it is molded 6min under 14MPa, then temperature is dropped to
Room temperature.
4th, analyze
Fig. 1 is embodiment 1 and comparative example 1, the 2 DSC exotherm when 5k/min lower the temperature, it can be seen that embodiment 1 and
Comparative example 1,2 is compared, and, substantially to elevated temperature excursions, that is, the polylactic acid of post anneal crystalline state is to poly- own interior for the crystallization temperature of polycaprolactone
Ester heterogeneous nucleation effect is more notable so that polycaprolactone crystalline rate accelerates, and interface compatibility improves, and this also fully proves can
To control polycaprolactone crystallization and two-phase interface bonding by regulating and controlling polylactic acid annealing history.
Fig. 2 is embodiment 1 and comparative example 1, load-deformation curve in drawing process for the 2 corresponding three kinds of materials.Stretching
Behavior is tested according to ASTM D638, and stretching speed is 50 mm/min, and under room temperature, record displacement is with the change of load.
Following table gives the mechanical performance index of corresponding embodiment 1 and comparative example 1,2 samples.
As seen from the above table：
Compared with pure polycaprolactone sample corresponding with comparative example 1, the Young's moduluss of the corresponding co-mixing system of embodiment 1 and tensile strength
All assume significant ascendant trend, when polylactic acid is annealed without cold crystallization（Comparative example 2）Although the Young's moduluss of material and
Tensile strength is also improved to some extent, but the intermingling material performance boost that can not show a candle to through annealing comes so aobvious
Write.This further demonstrates polylactic acid to anneal under the cold crystallization temperature setting, more notable to polycaprolactone reinforced effects, altogether
The mechanical property of mixed material is also more excellent.
Claims (2)
1. a kind of preparation method of high performance polycaprolactone/polylactic acid blend material it is characterised in that first by polycaprolactone and
Polylactic acid is placed in banbury, under 170 DEG C of temperature conditionss, melt blending, and obtain the blend of polycaprolactone and polylactic acid, then
Described blend is warming up to 175 DEG C, under conditions of pressure is 10～15MPa, is cooled to 100～145 DEG C of annealing 3～12h,
Finally it is cooled to room temperature, obtain final product highly crystalline, high performance polycaprolactone/polylactic acid blend material.
2. method according to claim 1 it is characterised in that：The mixing quality of described polycaprolactone and polylactic acid is than for 1
～4: 1.
Priority Applications (1)
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| CN201610827769.XA CN106380804A (en) | 2016-09-18 | 2016-09-18 | Preparation method of high-performance polycaprolactone/polylactic acid blend material |
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| CN201610827769.XA CN106380804A (en) | 2016-09-18 | 2016-09-18 | Preparation method of high-performance polycaprolactone/polylactic acid blend material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102320A (en) * | 2017-12-06 | 2018-06-01 | 海南大学 | A kind of preparation method of polylactic acid and caprolactone/polyoxymethylene blends |
| CN113403750A (en) * | 2021-06-28 | 2021-09-17 | 运鸿集团股份有限公司 | Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask |
| WO2024032073A1 (en) * | 2022-08-10 | 2024-02-15 | 浙江旺林生物科技有限公司 | Polylactic acid/polycaprolactone/plant carbon black composite material and preparation method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421285A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Environment-friendly heat-resistant polylactic acid and preparation method thereof |
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2016
- 2016-09-18 CN CN201610827769.XA patent/CN106380804A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421285A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Environment-friendly heat-resistant polylactic acid and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| QIAOLIAN LV ET AL.: "Crystallization of poly(3-caprolactone) in its immiscible blend with polylactide: insight into the role of annealing histories", 《RSC ADV.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102320A (en) * | 2017-12-06 | 2018-06-01 | 海南大学 | A kind of preparation method of polylactic acid and caprolactone/polyoxymethylene blends |
| CN108102320B (en) * | 2017-12-06 | 2019-11-12 | 海南大学 | A kind of preparation method of polylactic acid and caprolactone/polyoxymethylene blends |
| CN113403750A (en) * | 2021-06-28 | 2021-09-17 | 运鸿集团股份有限公司 | Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask |
| CN113403750B (en) * | 2021-06-28 | 2022-02-25 | 运鸿集团股份有限公司 | Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask |
| WO2024032073A1 (en) * | 2022-08-10 | 2024-02-15 | 浙江旺林生物科技有限公司 | Polylactic acid/polycaprolactone/plant carbon black composite material and preparation method therefor |
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