CN106589874B - The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose - Google Patents
The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose Download PDFInfo
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- CN106589874B CN106589874B CN201710000813.4A CN201710000813A CN106589874B CN 106589874 B CN106589874 B CN 106589874B CN 201710000813 A CN201710000813 A CN 201710000813A CN 106589874 B CN106589874 B CN 106589874B
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- acid ester
- butanoic 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose, is related to the technical field being modified to poly- (beta-hydroxy-butanoic acid ester).Pla-pcl, ethyl cellulose and poly- (beta-hydroxy-butanoic acid ester) are placed in mixer, to get poly- (beta-hydroxy-butanoic acid ester) composite material of modification after melt blending mediates plasticizing.The present invention is using pla-pcl as toughening element, and using ethyl cellulose as enhancing component, the toughness and intensity of poly- (beta-hydroxy-butanoic acid ester) can be effectively improved by mediating plasticizing through melt blending.
Description
Technical field
The present invention relates to the technical fields being modified to poly- (beta-hydroxy-butanoic acid ester).
Background technique
Natural high molecular material cellulose is received more and more attention due to its extensive source, and cellulose is certainly
The most abundant biodegradable material in right boundary.Main source is plant, and animal, specific fungi, seaweed, bacterium can also generate
Cellulose.Cellulose has that at low cost, density is low, source is wide, renewable, specific strength is high, specific modulus is high, good biocompatibility etc.
Advantage.Cellulose is widely used in enhancing the neck such as polymer composites, medicine, food additives, papermaking, building materials, coating
Domain.
Poly- (beta-hydroxy-butanoic acid ester) material of the biodegradable material of Microbe synthesis is due to its good biodegradable
Performance can be decomposed utilization as energy substance by multiple-microorganism in nature, be finally decomposed to carbon dioxide and water, no
Any pollution can be caused to environment.The highly crystalline characteristic of poly- (beta-hydroxy-butanoic acid ester) shows as its mechanical property hard and crisp.
Chemically synthesized biodegradable material polycaprolactone has good toughness, and the soft and tough characteristic of polycaprolactone just can be with
Poly- (beta-hydroxy-butanoic acid ester) is complementary, therefore is to obtain by poly- (beta-hydroxy-butanoic acid ester) and polycaprolactone, cellulosic material melt blending
The simple and easy method for the biodegradable material that must be had excellent performance.
The existing physical modification method for poly- (beta-hydroxy-butanoic acid ester) mainly utilizes polyester rigid or flexible
Poly- (beta-hydroxy-butanoic acid ester) is modified.Poly- (beta-hydroxy-butanoic acid ester) is modified with the polyester of rigidity, although intensity meeting
It improves, but resulting materials toughness is very poor.And it is modified to poly- (beta-hydroxy-butanoic acid ester) with polyester flexible, in resulting materials toughness
It rises, but intensity can become smaller.
Summary of the invention
The present invention provides a kind of method of ethyl cellulose modified poly- (beta-hydroxy-butanoic acid ester) in view of the foregoing drawbacks, to improve
The toughness and intensity of poly- (beta-hydroxy-butanoic acid ester).
The technical scheme is that pla-pcl, ethyl cellulose and poly- (beta-hydroxy-butanoic acid ester) are placed in mixer
In, to get poly- (beta-hydroxy-butanoic acid ester) composite material of modification after melt blending mediates plasticizing.
The present invention is using pla-pcl as toughening element, using ethyl cellulose as enhancing component, through melt blending
The toughness and intensity of poly- (beta-hydroxy-butanoic acid ester) can be effectively improved by mediating plasticizing.
Further, the mixing mass ratio of pla-pcl of the present invention and poly- (beta-hydroxy-butanoic acid ester) is 10: 90~50:
50.For modified poly- (beta-hydroxy-butanoic acid ester) composite material, not all components can expire than lower blend obtained
Condition of the sufficient polycaprolactone as toughener.First of all, it is necessary to could still be sent out in this way based on poly- (beta-hydroxy-butanoic acid ester) component
Wave poly- (beta-hydroxy-butanoic acid ester) intrinsic advantage；Secondly, the very few toughening effect of polycaprolactone additional amount is not significant；Therefore pla-pcl
When mixing mass ratio with poly- (beta-hydroxy-butanoic acid ester) is 10: 90~50: 50, preferable toughening effect can be reached.
The mixing mass ratio of the ethyl cellulose and poly- (beta-hydroxy-butanoic acid ester) is 1: 99~20: 80.For reinforcing agent
For ethyl cellulose, additional amount is too big, and the effective viscosity of system significantly increases, and hinders the movement of strand, is unfavorable for poly- (β-
Butyric ester) matrix machine-shaping.And ethyl cellulose dosage excessively will cause interface defect and increase, and therefore, second
Base cellulose dosage can be only achieved optimal enhancing effect for the 1~20% of poly- (beta-hydroxy-butanoic acid ester)/polycaprolactone mixed matrix
Fruit.
In addition, the smelting temperature in mixer of the present invention is 180 DEG C, rotor speed is 50~100 rpm, and melting is altogether
It does time as 5min.Rotor speed is too small to be unfavorable for polycaprolactone and ethyl cellulose is uniformly dispersed, excessive to will cause poly- (β-hydroxyl
Base butyrate) matrix degradation, therefore 50~100 rpm are more suitable for；The melt blending time is too short to be unfavorable for polycaprolactone and second
Base cellulose is uniformly dispersed, too long to will also result in poly- (beta-hydroxy-butanoic acid ester) matrix degradation, therefore controlling is that 5min is more suitable for.
Poly- (beta-hydroxy-butanoic acid ester) fusing point is 175 DEG C, and degradable under high temperature, process window is relatively narrow.It is used as processing temperature using 180 DEG C,
Both the melt viscosity that poly- (beta-hydroxy-butanoic acid ester) can have been reduced makes poly- (beta-hydroxy-butanoic acid ester) and pla-pcl, ethyl cellulose
Uniformly mixing, and can degrade to avoid poly- (beta-hydroxy-butanoic acid ester).
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of material prepared by comparative example 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of material prepared by comparative example 3.
Fig. 3 is the tensile strength performance figure of material made of comparative example 1,2,3.
Fig. 4 is the impact strength performance map of material made of comparative example 1,2,3.
Fig. 5 is the tensile strength performance figure of product made of embodiment 1,2.
Fig. 6 is the impact strength performance map of product made of embodiment 1,2.
Specific embodiment
The present invention is further explained combined with specific embodiments below.
With reference to embodiments, technical solution of the present invention is described further, but the purpose of these embodiments is not
It is to limit the scope of the invention.In these embodiments, unless otherwise stated, all percentage compositions are by weight.
One, each material is prepared:
Comparative example 1:
1, poly- first (beta-hydroxy-butanoic acid ester) is placed in a vacuum drying oven drying for 24 hours, is cooled to room temperature, by poly- (beta-hydroxy
Butyrate) it is placed in mixer, control mixer temperature is 180 DEG C, and rotor speed is 50-100 rpm, 5 min of melting mixing
Afterwards to get arrive pure poly- (beta-hydroxy-butanoic acid ester) material.
2, discharging is injected into standard dog bone (mm × 2 of 32 mm × 4 mm) and standard rectangular using miniature injection machine
(mm × 4 of 80 mm × 10 mm) batten is used for the test of tensile property and impact property.Injection technique are as follows: barrel temperature 180
DEG C, 40 DEG C of mold temperature, 600 bar of injection pressure, 500 bar of dwell pressure.
Comparative example 2:
1, poly- (beta-hydroxy-butanoic acid ester) and polycaprolactone drying in vacuum oven is respectively placed in first for 24 hours, to be cooled to
Poly- (beta-hydroxy-butanoic acid ester) and polycaprolactone are placed in mixer by room temperature by 70: 30 mass ratio that feeds intake, and control mixer temperature
Degree is 180 DEG C, and rotor speed is 50~100 rpm, arrives Polycaprolactone modified poly- (beta-hydroxy after 5 min of melt blending
Butyrate) composite material.
2, discharging is injected into standard dog bone (mm × 2 of 32 mm × 4 mm) and standard rectangular using miniature injection machine
(mm × 4 of 80 mm × 10 mm) batten is used for the test of tensile property and impact property.Injection technique are as follows: barrel temperature 180
DEG C, 40 DEG C of mold temperature, 600 bar of injection pressure, 500 bar of dwell pressure.
Comparative example 3:
1, poly- (beta-hydroxy-butanoic acid ester) and polycaprolactone drying in vacuum oven is respectively placed in first for 24 hours, to be cooled to
Poly- (beta-hydroxy-butanoic acid ester) and polycaprolactone are placed in mixer by room temperature by 50: 50 mass ratio that feeds intake, and control mixer temperature
Degree is 180 DEG C, and rotor speed is 90 rpm, arrives Polycaprolactone modified poly- (beta-hydroxy-butanoic acid after 5 min of melt blending
Ester) composite material.
2, discharging is injected into standard dog bone (mm × 2 of 32 mm × 4 mm) and standard rectangular using miniature injection machine
(mm × 4 of 80 mm × 10 mm) batten is used for the test of tensile property and impact property.Injection technique are as follows: barrel temperature 180
DEG C, 40 DEG C of mold temperature, 600 bar of injection pressure, 500 bar of dwell pressure.
Embodiment 1:
1, poly- (beta-hydroxy-butanoic acid ester), polycaprolactone, ethyl cellulose are respectively placed in vacuum oven first dry
For 24 hours, it is cooled to room temperature, sets poly- (beta-hydroxy-butanoic acid ester), polycaprolactone and ethyl cellulose by 70: 30: 1 mixing mass ratio
In mixer, control mixer temperature be 180 DEG C, rotor speed be 50-100 rpm, 5 min of melt blending to get arrive second
Cellulose modified poly- (the beta-hydroxy-butanoic acid ester)/pla-pcl composite material of base.
2, discharging is injected into standard dog bone (mm × 2 of 32 mm × 4 mm) and standard rectangular using miniature injection machine
(mm × 4 of 80 mm × 10 mm) batten is used for the test of tensile property and impact property.Injection technique are as follows: barrel temperature 180
DEG C, 40 DEG C of mold temperature, 600 bar of injection pressure, 500 bar of dwell pressure.
Embodiment 2:
1, poly- (beta-hydroxy-butanoic acid ester), polycaprolactone, ethyl cellulose are respectively placed in vacuum oven first dry
For 24 hours, it is cooled to room temperature, sets poly- (beta-hydroxy-butanoic acid ester), polycaprolactone and ethyl cellulose by 50: 50: 1 mixing mass ratio
In mixer, control mixer temperature be 180 DEG C, rotor speed be 50-100 rpm, 5 min of melt blending to get arrive second
Cellulose modified poly- (the beta-hydroxy-butanoic acid ester)/polycaprolactone composite material of base.
2, discharging is injected into standard dog bone (mm × 2 of 32 mm × 4 mm) and standard rectangular using miniature injection machine
(mm × 4 of 80 mm × 10 mm) batten is used for the test of tensile property and impact property.Injection technique are as follows: barrel temperature 180
DEG C, 40 DEG C of mold temperature, 600 bar of injection pressure, 500 bar of dwell pressure.
Two, it analyzes:
The scanning electron microscope (SEM) photograph of product made of the respectively comparative example 2,3 of Fig. 1,2, as can be seen from the figure polycaprolactone is uniform
It is dispersed in poly- (beta-hydroxy-butanoic acid ester) matrix, and the size of dispersed phase polycaprolactone depends on the variation of content.
The tensile strength and impact strength performance map of product made of the respectively comparative example 1,2,3 of Fig. 3,4.It can be seen that: gather oneself
The addition of lactone improves the mechanical property of poly- (beta-hydroxy-butanoic acid ester), and when polycaprolactone content is 30%, tensile strength is improved
20%, from 27.5 MPa it is increased to 31.1 MPa.When polycaprolactone content is 50%, the impact strength of composite material is from 6.27
kJ/m2It is increased to 9.16 kJ/m2。
The tensile strength and impact strength performance map of product made of the respectively embodiment 1,2 of Fig. 5,6.It can be seen that: to poly- (β-
Butyric ester) 1% ethyl cellulose is added in/polycaprolactone composite material after, poly- (beta-hydroxy-butanoic acid ester)/polycaprolactone/second
The tensile strength of 70/30/1 sample of base cellulose is improved to 36.2 MPa, and poly- (beta-hydroxy-butanoic acid ester)/polycaprolactone/ethyl is fine
The impact strength for tieing up plain 50/50/1 sample is improved to 20.5 kJ/m2。
Claims (2)
1. the preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose, it is characterised in that by pla-pcl,
Ethyl cellulose and poly- (beta-hydroxy-butanoic acid ester) are placed in mixer, to get the poly- (β-hydroxyl of modification after melt blending mediates plasticizing
Base butyrate) composite material；The mixing mass ratio of poly- (beta-hydroxy-butanoic acid ester), polycaprolactone and ethyl cellulose is 50:
50∶1。
2. the preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose according to claim 1,
It is characterized in that smelting temperature in the mixer is 180 DEG C, rotor speed is 50~100 rpm, and the melt blending time is
5min。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710000813.4A CN106589874B (en) | 2017-01-03 | 2017-01-03 | The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose |
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| CN201710000813.4A CN106589874B (en) | 2017-01-03 | 2017-01-03 | The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose |
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| CN106589874B true CN106589874B (en) | 2018-12-11 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898324A (en) * | 2003-12-22 | 2007-01-17 | 伊斯曼化学公司 | Polymer blends with improved rheology and improved unnotched impact strength |
| CN105623216A (en) * | 2016-02-25 | 2016-06-01 | 扬州大学 | Preparing method for modified poly(beta-hydroxybutyrate) composite |
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2017
- 2017-01-03 CN CN201710000813.4A patent/CN106589874B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898324A (en) * | 2003-12-22 | 2007-01-17 | 伊斯曼化学公司 | Polymer blends with improved rheology and improved unnotched impact strength |
| CN105623216A (en) * | 2016-02-25 | 2016-06-01 | 扬州大学 | Preparing method for modified poly(beta-hydroxybutyrate) composite |
Non-Patent Citations (1)
| Title |
|---|
| Processing and characterization of binary poly(hydroxybutyrate) (PHB) and poly(caprolactone)(PCL) blends with improved impact properties;D. Garcia-Garcia et al.;《Polym. Bull.》;20160407;第73卷;第3335页第9-21行、表1、第3338页图1 * |
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