CN105623216A - Preparing method for modified poly(beta-hydroxybutyrate) composite - Google Patents
Preparing method for modified poly(beta-hydroxybutyrate) composite Download PDFInfo
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- CN105623216A CN105623216A CN201610104492.8A CN201610104492A CN105623216A CN 105623216 A CN105623216 A CN 105623216A CN 201610104492 A CN201610104492 A CN 201610104492A CN 105623216 A CN105623216 A CN 105623216A
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- acid ester
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention provides a preparing method for a modified poly(beta-hydroxybutyrate) composite and relates to the technical field of modification of poly(beta-hydroxybutyrate) and the technical field of degradable plastic.The preparing method comprises the steps that ethylene cellulose (EC) serves as a dispersing phase and is subjected to melt blending with poly(beta-hydroxybutyrate) (PHB) with a proper technology, EC is evenly dispersed in a biodegradable polyester PHB matrix, and a high-performance green polymer material is prepared.In a cellulose-based composite, EC influences the crystal habit and crystallization rate of the matrix polymer, even changes the compatibility and interfacial properties of incompatible blend systems and finally changes the ultimate performance of the matrix polymer, and thus the mechanical property, the crystallization degree and the crystal habit of the composite are controlled.
Description
Technical field
The present invention relates to poly-(beta-hydroxy-butanoic acid ester) technical field of modification, be directed to degradation plastic technical field.
Background technology
In recent years, bio-based polymers material is used in different fields to alleviate the problem of environmental pollution that non-degradable plastic brings.
Poly-(beta-hydroxy-butanoic acid ester) (PHB) has attracted to pay close attention to widely as the Biodegradable material of Microbe synthesis, and PHB is that a kind of degree of crystallinity is high, crystalline rate is fast, the material that more crisp and degradation rate is slow, which has limited the use of PHB. PHB is not as high molecular weight relatively, also makes it show relatively low melt strength in the course of processing, which also limits the use scope that PHB material is final.
Cellulosic-based material due to its widely raw material sources and eco-friendly characteristic and by big quantity research, ethyl cellulose (EC), as typical cellulose derivative, has thermoplasticity, high mechanical properties, good thermostability and heat stability.
Summary of the invention
The present invention is directed to the preparation method that drawbacks described above provides the composite of a kind of poly-(beta-hydroxy-butanoic acid ester) modified based on ethyl cellulose, to change the compatibility and the interfacial property of incompatible co-mixing system, finally change the final performance of matrix polymer.
The technical scheme is that: dry ethyl cellulose (EC) is placed in banbury with poly-(beta-hydroxy-butanoic acid ester) (PHB), when temperature at banbury is 180 DEG C, rotor speed is 90rpm, melt blending obtains the composite of ethyl cellulose modified poly-(beta-hydroxy-butanoic acid ester).
The present invention utilizes ethyl cellulose (EC) as dispersion phase, adopt suitable technique and poly-(beta-hydroxy-butanoic acid ester) (PHB) melt blending, EC is made to be dispersed in biodegradable polyesters PHB matrix, prepare High-performance green polymeric material, in cellulose base composite, EC affects crystal habit and the crystalline rate of matrix polymer, even change the compatibility and the interfacial property of incompatible co-mixing system, finally change the final performance of matrix polymer, thus controlling the mechanical property of composite, degree of crystallinity and crystal habit.
Further, in order to make the weight/mass percentage composition of EC in composite can regulate in 1 ~ 20%, the mass ratio that feeds intake of described ethyl cellulose and poly-(beta-hydroxy-butanoic acid ester) is 1��25: 100. When in composite, EC mass fraction is 1%, the mechanical property of composite is best. When in composite, EC mass fraction is 20%, there is percolation in composite. And when in composite, EC mass fraction is 1��20%, degree of crystallinity and the crystal habit of composite change.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite of poly-(beta-hydroxy-butanoic acid ester) that ethyl cellulose prepared by the embodiment of the present invention 1 modifiies.
Fig. 2 is the scanning electron microscope (SEM) photograph of the composite of poly-(beta-hydroxy-butanoic acid ester) that ethyl cellulose prepared by the embodiment of the present invention 3 modifiies.
Fig. 3 is embodiment 1, embodiment 2, the tensile strength performance comparison diagram of the composite of poly-(beta-hydroxy-butanoic acid ester) that the ethyl cellulose of the preparation of embodiment 3 and comparative example 1 is modified.
Fig. 4 is embodiment 1, embodiment 2, the impact strength performance comparison figure of the composite of poly-(beta-hydroxy-butanoic acid ester) that the ethyl cellulose of the preparation of embodiment 3 and comparative example 1 is modified.
Fig. 5 is embodiment 1, embodiment 2, the storage modulus performance comparison figure of the composite of poly-(beta-hydroxy-butanoic acid ester) that the ethyl cellulose of embodiment 3 and comparative example 1 preparation modifiies.
Fig. 6 is embodiment 1, embodiment 2, the loss modulus performance comparison figure of the composite of poly-(beta-hydroxy-butanoic acid ester) that the ethyl cellulose of embodiment 3 and comparative example 1 preparation modifiies.
Fig. 7 is the composite spherulitic morphology figure at different temperatures of modified poly-(beta-hydroxy-butanoic acid ester) of the ethyl cellulose prepared of the present invention.
Detailed description of the invention
The present invention is expanded on further below in conjunction with specific embodiment.
Below in conjunction with embodiment, technical scheme is described further, but these embodiments be not intended to limit the scope of the invention. In these embodiments, unless otherwise indicated, all percentage compositions are all by weight.
One, production example:
Embodiment 1:
1, first ethyl cellulose (EC) is placed in vacuum drying oven with poly-(beta-hydroxy-butanoic acid ester) (PHB), dry 24h under 60 DEG C of conditions, it is cooled to room temperature, EC and the PHB that mass ratio is 1: 99 is placed in banbury, controlling banbury temperature is 180 DEG C, rotor speed is 90rpm, after melt blending 5min, namely obtains the composite of ethyl cellulose modified poly-(beta-hydroxy-butanoic acid ester).
2, use miniature injection machine that discharging is injected into the test for tensile property and impact property of standard dog bone (32mm �� 4mm �� 2mm) and standard rectangular (80mm �� 10mm �� 4mm) batten. Injection technique is: barrel temperature 180 DEG C, mold temperature 30 DEG C, injection pressure 600bar, dwell pressure 500bar.
Embodiment 2:
1, first EC and PHB is placed in vacuum drying oven, dry 24h under 60 DEG C of conditions, it is cooled to room temperature, EC and the PHB that mass ratio is 5: 95 is placed in banbury, controlling banbury temperature is 180 DEG C, rotor speed is 90rpm, after melt blending 5min, namely obtains the composite of ethyl cellulose modified poly-(beta-hydroxy-butanoic acid ester).
2, use miniature injection machine that discharging is injected into the test for tensile property and impact property of standard dog bone (32mm �� 4mm �� 2mm) and standard rectangular (80mm �� 10mm �� 4mm) batten. Injection technique is: barrel temperature 180 DEG C, mold temperature 30 DEG C, injection pressure 600bar, dwell pressure 500bar.
Embodiment 3:
1, first EC and PHB is placed in vacuum drying oven, dry 24h under 60 DEG C of conditions, it is cooled to room temperature, EC and the PHB that mass ratio is 20: 80 is placed in banbury, controlling banbury temperature is 180 DEG C, rotor speed is 90rpm, after melt blending 5min, namely obtains the composite of ethyl cellulose modified poly-(beta-hydroxy-butanoic acid ester).
2, use miniature injection machine that discharging is injected into the test for tensile property and impact property of standard dog bone (32mm �� 4mm �� 2mm) and standard rectangular (80mm �� 10mm �� 4mm) batten. Injection technique is: barrel temperature 180 DEG C, mold temperature 30 DEG C, injection pressure 600bar, dwell pressure 500bar.
Comparative example 1:
1, first PHB is placed in vacuum drying oven, and under 60 DEG C of conditions, dry 24h, is cooled to room temperature, being placed in banbury by PHB, controlling banbury temperature is 180 DEG C, and rotor speed is 90rpm, after melting mixing 5min, namely obtain pure poly-(beta-hydroxy-butanoic acid ester) material.
2, use miniature injection machine that discharging is injected into the test for tensile property and impact property of standard dog bone (32mm �� 4mm �� 2mm) and standard rectangular (80mm �� 10mm �� 4mm) batten. Injection technique is: barrel temperature 180 DEG C, mold temperature 30 DEG C, injection pressure 600bar, dwell pressure 500bar.
Two, analyze:
Fig. 1,2 respectively composites that embodiment 1 and embodiment 3 obtain scanning electron microscope (SEM) photograph, as can be seen from the figure EC is dispersed in PHB matrix, and the size of dispersion phase EC does not rely on the change of content.
Effectively improving the mechanical property of PHB from the addition of the mechanical property comparison diagram of Fig. 3 and Fig. 4: EC, when EC content is 1%, hot strength improves 22%, brings up to 33.3MPa from 27.5MPa. Under this content, the impact strength of composite is also the highest.
From the rheological property comparison diagram of Fig. 5 and Fig. 6: the modulus of composite significantly improves along with the increase of EC content, when EC content reaches 20%, the storage modulus of the low frequency range of system is higher than loss modulus, occurs exceeding and oozes.
Fig. 7 is embodiment 1, embodiment 2, embodiment 3 and comparative example 1 spherulitic morphology figure at different temperatures. It can be seen from figure 7 that the spherulitic morphology of PHB is transformed into Ring-banded spherulite along with the change of temperature from footpath pencil. The addition of EC makes the spherocrystal spacing of Ring-banded spherulite diminish.
Following table is embodiment 1, embodiment 2, the composite that embodiment 3 and comparative example 1 are respectively prepared means of differential scanning calorimetry data under the temperature rate of 5 DEG C/min.
In upper table,T c: crystallization temperature;T m: melt temperature; DH c: crystallization enthalpy; DH m: melting enthalpy.
As seen from the above table: the crystallization temperature of composite reduces along with the rising of EC content, and the addition of EC reduces the degree of crystallinity of composite.
Claims (2)
1. the preparation method of poly-(beta-hydroxy-butanoic acid ester) composite one kind modified, it is characterized in that being placed in banbury by dry ethyl cellulose with poly-(beta-hydroxy-butanoic acid ester), when temperature at banbury is 180 DEG C, rotor speed is 90rpm, melt blending obtains the composite of ethyl cellulose modified poly-(beta-hydroxy-butanoic acid ester).
2. the preparation method of modified poly-(beta-hydroxy-butanoic acid ester) composite according to claim 1, it is characterised in that the mass ratio that feeds intake of described ethyl cellulose and poly-(beta-hydroxy-butanoic acid ester) is 1��25: 100.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589874A (en) * | 2017-01-03 | 2017-04-26 | 扬州大学 | Preparation method for ethyl cellulose modified poly(beta-polyhydroxybutyrate) composite material |
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| CN101503521A (en) * | 2009-03-05 | 2009-08-12 | 上海交通大学 | Preparation of high-strength high-ductility biodegradable composite material |
| CN102219988A (en) * | 2010-04-14 | 2011-10-19 | 美亚无纺布工业有限公司 | Biodegradable recycling material |
| CN102250389A (en) * | 2011-06-17 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof |
| CN102665635A (en) * | 2009-12-23 | 2012-09-12 | 金伯利-克拉克环球有限公司 | Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester |
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- 2016-02-25 CN CN201610104492.8A patent/CN105623216A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503521A (en) * | 2009-03-05 | 2009-08-12 | 上海交通大学 | Preparation of high-strength high-ductility biodegradable composite material |
| CN102665635A (en) * | 2009-12-23 | 2012-09-12 | 金伯利-克拉克环球有限公司 | Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester |
| CN102219988A (en) * | 2010-04-14 | 2011-10-19 | 美亚无纺布工业有限公司 | Biodegradable recycling material |
| CN102250389A (en) * | 2011-06-17 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106589874A (en) * | 2017-01-03 | 2017-04-26 | 扬州大学 | Preparation method for ethyl cellulose modified poly(beta-polyhydroxybutyrate) composite material |
| CN106589874B (en) * | 2017-01-03 | 2018-12-11 | 扬州大学 | The preparation method of modified poly- (beta-hydroxy-butanoic acid ester) composite material of ethyl cellulose |
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