CN114031912A - Enzyme-synthesized nano-cellulose/PHBV composite material and preparation method thereof - Google Patents
Enzyme-synthesized nano-cellulose/PHBV composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001746 injection moulding Methods 0.000 claims abstract description 48
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 30
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 108010077004 Cellodextrin phosphorylase Proteins 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims abstract description 5
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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
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- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention relates to the field of high polymer materials, in particular to an enzyme synthesized nano cellulose/PHBV composite material and a preparation method thereof, which comprises the following steps: after the raw materials of the enzyme-synthesized nano-cellulose and PHBV are dried in vacuum, the raw materials are added into an injection molding device for injection molding to obtain an enzyme-synthesized nano-cellulose/PHBV composite material product with high mechanical property; the enzyme synthesized nano-cellulose is prepared by glucose or cellobiose through the catalysis of cellodextrin phosphorylase; the weight average molecular weight of the PHBV raw material is 10000-700000, and the HV content is 1-40%; the content of the enzyme synthesized nano-cellulose in the composite material product in PHBV is 0.1-8 wt%. The prepared PHBV composite material has tensile strength of more than 36MPa and elongation at break of more than 5.7 percent.
Description
Technical Field
The invention relates to the field of biodegradable polymer composite materials, in particular to an enzyme-synthesized nano-cellulose/PHBV composite material and a preparation method thereof.
Background
The poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV for short) is a thermoplastic polymer material prepared by using starch as a raw material and applying a biological fermentation technology, has the advantages of good biodegradability and biocompatibility and the like, and has wide application prospect in various fields of biology, medicine, degradable packaging materials and the like. However, PHBV has a low crystallization rate and a high crystallinity, and tends to form large-sized spherulites. The PHBV has the defects of brittle texture, poor impact resistance and the like due to the fact that a plurality of annular cracks are formed by outwards expanding the spherulites as centers, so that the application is greatly limited and the PHBV needs to be modified. Cellulose is the most abundant natural high molecular material with biodegradability in nature, and the excellent physical and chemical properties also make the cellulose an important industrial raw material, and the cellulose is applied to the fields of paper making, food packaging, fabrics, ropes and the like. And with the increasing scarcity of resources and the gradual attention of people to environmental protection, the cheap and high-quality green renewable resource has wider application prospect. The nano-cellulose serving as a novel nano-material not only has the characteristic of high specific surface area of a common nano-material, but also has the advantages of low density, low cost, high strength, reproducibility, biodegradation and the like, and is widely applied to coatings, electronic equipment and composite materials.
The realization of high performance and low cost of polymer materials by utilizing many excellent properties of nanocellulose has been a research focus. Bhardwaj adopts natural cellulose to modify PHBV, so that the toughness of the PHBV is improved, and the elongation at break of the PHBV reaches 10% (biomacromolecules 2006, 7, 2044-. However, natural nano-cellulose can only be treated by mechanical crushing and strong corrosive or oxidative reagents, so that the preparation technology is complicated, and the used reagents cause pollution to the environment to a certain extent.
Cellulose can be prepared by the condensation of the a-D-glucose-1-phosphate monomer (aG1P) with the hydroxyl group at glucose position 4 by the catalytic action of an in vitro enzyme, cellodextrin phosphorylase (CDP). The whole preparation process is completed in one step, the reaction conditions are mild, the environment is protected, the defects of the traditional cellulose preparation method are effectively overcome, and the method is a cellulose preparation method which is expected to realize large-scale production. In addition, the nanocellulose prepared by the enzyme catalysis method has good biocompatibility and degradability, so the nanocellulose has great application potential in polymer composite materials. At present, the research on the reinforcing aspect of the crystalline biodegradable polymer of the novel cellulose material is not reported, the reinforcing effect of the novel cellulose material in PHBV is researched, the preparation process and the performance of the enzyme-synthesized nano cellulose/PHBV composite material are optimized, and the novel biodegradable composite material product is favorably developed.
The information disclosed in the background section is only for background to aid in understanding the invention and should not be taken as an acknowledgement or any way to imply that the information forms part of the prior art that is already known to a person skilled in the art.
Disclosure of Invention
The invention aims to solve the problem of low mechanical property of the existing PHBV plastic product, and provides an enzyme-synthesized nano-cellulose/PHBV composite material with high mechanical property and a preparation method thereof.
The invention adopts an in vitro enzyme catalysis method to prepare the nano-cellulose, the enzyme synthesized nano-cellulose not only has environment-friendly reaction conditions and simple preparation process, but also has excellent chemical, mechanical and physical properties, and simultaneously the cellulose has excellent nucleation and mechanical property strengthening effects on the PHBV biodegradable polymer, and the defect of high brittleness of the PHBV is overcome by doping the enzyme synthesized nano-cellulose into a PHBV matrix through a specific injection molding process. Because a large amount of carbonyl exists in the cellulose molecular chain, the cellulose molecular chain and the carbonyl on the PHBV molecular chain can form a strong hydrogen bond effect, and the dispersibility of the cellulose in a matrix is regulated and controlled by regulating the content of the cellulose, so that the crystallization capacity of a product is influenced, and the mechanical property of the PHBV composite material is improved.
After intensive research, the inventors of the present application found that: by using the enzyme-synthesized nanocellulose, an enzyme-synthesized nanocellulose/PHBV composite material having high mechanical properties can be prepared, and the present invention has been accomplished thereby.
The technical scheme adopted by the invention is as follows:
a preparation method of an enzyme-synthesized nano-cellulose/PHBV composite material comprises the following specific steps:
after the raw materials of the enzyme-synthesized nano-cellulose and PHBV are dried in vacuum, the raw materials are added into an injection molding device for injection molding to obtain an enzyme-synthesized nano-cellulose/PHBV composite material product with high mechanical property;
the enzyme synthesized nano-cellulose is prepared by glucose or cellobiose through the catalysis of cellodextrin phosphorylase;
the weight average molecular weight of the PHBV raw material is 10000-700000, and the HV content is 1-40%;
the content of the enzyme synthesized nano-cellulose in the composite material product in PHBV is 0.1-8 wt%.
The injection molding machine for injection molding in the present invention is not particularly limited, and a screw type injection molding machine, a ram type injection molding machine, a screw preplasticizing ram type injection molding machine, and the like can be cited, and a screw type injection molding machine is preferable, and the screw type injection molding machine is widely used, and is superior in plasticization and kneading property to other injection molding machines.
Preferably, the screw temperature for the injection molding processing of the composite material in the invention is 170-200 ℃. The temperature of the screw is too low, the PHBV is not completely melted, the viscosity of the system is too high, and a ground opening is easy to block; the screw temperature is too high, the PHBV system viscosity is too low, the product is not easy to produce, and the product is easy to degrade, so that the strength of the product is reduced.
Preferably, the screw rotating speed of the composite material injection molding processing is 50-150 r/min. The rotating speed of the screw is too low, the shearing force is small, the dispersion is not uniform, and the residence time is too long, so that the production efficiency is influenced; the rotating speed of the screw is too high, the shearing force is larger, thermal degradation is easily caused, the retention time is shortened, and the mixing is not uniform.
Preferably, the temperature of the material passing through the nozzle for injection molding processing of the composite material is 170-200 ℃, the injection pressure is 150-300MPa, the pressure maintaining pressure is 100-200MPa, the pressure maintaining time is 10-100s, and the mold temperature is 50-70 ℃. Under the injection molding condition, the PHBV is easy to process and less in degradation, the enzymatic synthetic cellulose has better dispersity in the PHBV, and the prepared injection molded product has the characteristics of stable size, excellent performance and the like.
Preferably, the enzymatic synthesis of nanocellulose according to the invention, preferably using cellobiose molecules, is carried out by catalysis by cellodextrin phosphorylase, mainly due to the low cost of the process and the availability of nanocellulose with a relatively uniform size.
Preferably, the PHBV raw material in the invention has the weight-average molecular weight of 20000-500000 and the HV content of 1-25%. The molecular weight of the PHBV raw material is lower, the viscosity of a system in the product forming and processing process is low, the product is difficult to produce, the binding force among molecular chains is increased along with the increase of the molecular weight, and the mechanical property and the heat-resistant deformation temperature of the product are increased; the PHBV raw material has an excessively high molecular weight, and the viscosity of a system in the processing process is excessively high, so that the blockage of a runner port is easily caused, and therefore, the weight average molecular weight range is preferably selected; when the HV content is too low, PHBV mainly contains PHB and exhibits significant brittleness, and when the HV content is too high, the effect of controlling the HV content in the HB crystal is limited, and therefore the above HV content range is preferable.
As a preferable scheme, the content of the enzyme synthesized nano-cellulose in PHBV is 0.5-5 wt%; when the content of the enzyme-synthesized nano-cellulose is too low, the dispersion in a PHBV matrix is limited, and the improvement on the mechanical property of the final composite material is limited; when the content of the enzyme-synthesized nanocellulose is too high, a large amount of cellulose is easy to agglomerate to cause stress concentration, and the mechanical property is greatly reduced, so the content range is preferably selected.
The shape of the injection molded article is not particularly limited, and it may be a plate or a pipe, and the thickness thereof is not particularly limited, and is usually 5 to 50 mm.
The above-mentioned PHBV product may further contain other auxiliaries, the type of the auxiliaries is not particularly limited, and may be one or more of an antioxidant, a lubricant, a heat stabilizer, etc., and the content of the additives is usually 0.01 to 1% by weight of PHBV, within this range, the auxiliaries function properly, but the effectiveness of the patent is not changed.
The enzymatic synthesis nano-cellulose/PHBV composite material is characterized in that the tensile property is tested according to the national standard GB/T1040.1-2006, the tensile strength is more than 36MPa, the elongation at break is more than 5.7%, the upper limit of the tensile strength is usually 40MPa, and the upper limit of the elongation at break is 10%.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the enzyme-synthesized nano-cellulose is simple and environment-friendly, effectively overcomes the defects of complex process and environmental pollution of used reagents in the traditional nano-cellulose preparation method, has better interface interaction with PHBV, and has excellent dispersibility in a PHBV matrix, so that the mechanical property of the composite material is improved, and the modification effect is obvious. The method has the advantages of simple process and low cost, ensures the improvement of mechanical properties, has the characteristic of biodegradability, and has good application prospect.
Drawings
FIG. 1 is the mechanical properties of the enzymatically synthesized nanocellulose/PHBV composites prepared in examples 1, 2, 3, 4 and comparative examples 1, 2;
FIG. 2 is a Differential Scanning Calorimetry (DSC) curve of the enzymatically synthesized nanocellulose/PHBV composites prepared in examples 1, 2, 3, 4 and comparative examples 1, 2;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of the enzymatically synthesized nanocellulose/PHBV composite materials prepared in examples 1, 2, 3, 4 and comparative examples 1, 2.
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples, but the present invention is not limited to the examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1:
weighing 1000g of PHBV powder with the weight-average molecular weight of 40000, wherein the HV content is 10%, the content of the enzymatically synthesized nano-cellulose is 1 wt%, and performing injection molding by using a screw injection molding machine, wherein the screw temperature of the injection molding machine is 180 ℃, the screw rotating speed is 50r/min, the temperature of the material passing through a nozzle is 180 ℃, the injection pressure is 250MPa, the pressure maintaining pressure is 180MPa, the pressure maintaining time is 50s, and the mold temperature is 50 ℃, thus preparing the enzymatically synthesized nano-cellulose/PHBV composite material.
Example 2:
weighing 1000g of PHBV powder with the weight-average molecular weight of 150000, wherein the HV content is 15%, the content of the enzymatically synthesized nanocellulose is 3 wt%, and performing injection molding by using a screw injection molding machine, wherein the screw temperature of the injection molding machine is 185 ℃, the screw rotating speed is 100r/min, the temperature of the material passing through a nozzle is 190 ℃, the injection pressure is 200MPa, the pressure maintaining pressure is 150MPa, the pressure maintaining time is 100s, the mold temperature is 60 ℃, and preparing the enzymatically synthesized nanocellulose/PHBV composite plate-shaped injection molding sample with the length of 250mm, the width of 100mm and the thickness of 25 mm.
Example 3:
weighing 1000g of PHBV powder with the weight-average molecular weight of 300000, wherein the HV content is 20%, the content of the enzymatically synthesized nano-cellulose is 5 wt%, and performing injection molding by using a screw injection molding machine, wherein the screw temperature of the injection molding machine is 190 ℃, the screw rotating speed is 150r/min, the temperature of the material passing through a nozzle is 200 ℃, the injection pressure is 250MPa, the pressure maintaining pressure is 180MPa, the pressure maintaining time is 50s, the mold temperature is 50 ℃, and preparing the enzymatically synthesized nano-cellulose/PHBV composite plate-shaped injection molding sample with the length of 250mm, the width of 100mm and the thickness of 25 mm.
Example 4:
weighing 1000g of PHBV powder with the weight-average molecular weight of 600000, wherein the HV content is 30%, the content of the enzyme-synthesized nano-cellulose is 5 wt%, and carrying out injection molding by using a screw injection molding machine, wherein the screw temperature of the injection molding machine is 180 ℃, the screw rotating speed is 100r/min, the temperature of a material passing through a nozzle is 200 ℃, the injection pressure is 200MPa, the pressure maintaining pressure is 150MPa, the pressure maintaining time is 100s, and the mold temperature is 70 ℃, so as to prepare an enzyme-synthesized nano-cellulose/PHBV composite material plate-shaped injection molding sample with the length of 250mm, the width of 100mm and the thickness of 25 mm.
Comparative example 1
Weighing 1000g of PHBV powder with the weight-average molecular weight of 100000, wherein the HV content is 10 percent, the content of the enzyme-synthesized nano-cellulose is 0.05 percent by weight, and carrying out injection molding by using a screw injection molding machine, wherein the temperature of a screw of the injection molding machine is 180 ℃, the rotating speed of the screw is 50r/min, the temperature of the material passing through a nozzle is 180 ℃, the injection pressure is 250MPa, the pressure maintaining pressure is 180MPa, the pressure maintaining time is 50s, the temperature of a mold is 50 ℃, and preparing the enzyme-synthesized nano-cellulose/PHBV composite material plate-shaped injection molding sample with the length of 250mm, the width of 100mm and the thickness of 25 mm.
Comparative example 2
Weighing 1000g of PHBV powder with the weight-average molecular weight of 600000, wherein the HV content is 30%, the content of the enzyme-synthesized nano-cellulose is 10 wt%, and carrying out injection molding by using a screw injection molding machine, wherein the screw temperature of the injection molding machine is 180 ℃, the screw rotating speed is 150r/min, the temperature of a material passing through a nozzle is 200 ℃, the injection pressure is 200MPa, the pressure maintaining pressure is 150MPa, the pressure maintaining time is 100s, and the mold temperature is 60 ℃, so as to prepare an enzyme-synthesized nano-cellulose/PHBV composite material plate-shaped injection molding sample with the length of 250mm, the width of 100mm and the thickness of 25 mm.
As can be seen from FIG. 1, the strength and elongation at break of the enzyme-synthesized nanocellulose/PHBV composite prepared in examples 1, 2, 3 and 4 are significantly improved compared with those of comparative examples 1 and 2, which indicates that the mechanical properties of the composite are greatly improved by adding a proper amount of enzyme-synthesized nanocellulose into the product of the examples. Therefore, the products of examples 1, 2, 3 and 4 can be analyzed to be more effective in promoting the improvement of the mechanical properties of the composite material than comparative examples 1 and 2.
As can be seen from FIG. 2, the crystallinity of the enzyme-synthesized nanocellulose/PHBV composite material prepared by the examples 1, 2, 3 and 4 is higher than that of the comparative examples 1 and 2, which shows that the product prepared by the examples has more perfect crystallization and better high temperature resistance; the crystallization temperature of the enzyme-synthesized nanocellulose/PHBV composite materials prepared in examples 1, 2, 3 and 4 is higher than that of comparative examples 1 and 2, which shows that the enzyme-synthesized nanocellulose as a nucleating agent increases nucleation points, increases nucleation density and has better mechanical properties with the increase of the content.
As can be seen from FIG. 3, the enzyme-synthesized nanocellulose/PHBV composite materials prepared in examples 1, 2, 3 and 4 have better dispersibility, while the composite material prepared in comparative example 1 has a lower cellulose content on the surface, and the composite material prepared in comparative example 2 has a large amount of cellulose agglomeration on the surface, which indicates that the dispersibility of cellulose in the PHBV matrix can be controlled by controlling the cellulose content, so that excellent mechanical properties can be obtained.
Table 1 shows the breaking strength, elongation at break, Young's modulus, melting point, crystallinity and crystallization temperature data of the enzyme-synthesized nanocellulose/PHBV composite material products prepared in examples 1, 2, 3 and 4 and comparative examples 1 and 2. As seen from the data in Table 1, the products of examples 1, 2, 3 and 4 have 23.2-34.5%, 7.6-82.7% and 8.5-25.4% respectively higher breaking strength, elongation at break and Young's modulus than those of comparative examples 1 and 2, which shows that the composite material with low content of enzyme synthesized nanocellulose has less dispersion and cannot play a role in strengthening and toughening when being acted by external force, while the composite material with high content of enzyme synthesized nanocellulose is used as a stress concentration point when being acted by external force due to the existence of aggregates, resulting in the reduction of mechanical properties. From the data in table 1, the melting point, crystallinity and crystallization temperature of examples 1, 2, 3 are higher than those of comparative example 1, indicating that the crystals formed in the products of the examples are more uniform, and that a suitable amount of enzymatically synthesized nanocellulose, as a nucleating agent, promotes the crystallization of PHBV to form more perfect crystals.
The results show that the embodiment can regulate the dispersion of the enzyme-synthesized nanocellulose in the PHBV and the interface interaction with the PHBV by controlling the process of the processing process of the enzyme-synthesized nanocellulose/PHBV composite material, particularly regulating the content of the enzyme-synthesized nanocellulose, the molecular weight of the PHBV, the screw temperature, the screw rotating speed and the injection molding temperature, thereby regulating the aggregation state structure of the composite material, improving the crystal structure in the product and effectively improving the strength and toughness of the composite material.
The screw temperature and the screw rotating speed adopted in the examples 2, 3 and 4 accord with the preferable ranges, and the mechanical property is better compared with that of the example 1, and the flowability is better and the cellulose is uniformly dispersed in the product processing process, so the mechanical property is better. Compared with the example 3, the injection molding process of the embodiment 2 is basically consistent, the content of the enzyme-synthesized cellulose is higher, the dispersion is better, and the content of the enzyme-synthesized nano-cellulose in the embodiment 3 meets the preferable range, so the mechanical property is better. Compared with example 4, the injection molding process and the content of the enzyme-synthesized nanocellulose of example 3 are basically consistent, but the PHBV weight-average molecular weight and the HV content of example 3 conform to the preferred ranges, so the mechanical properties are better. Therefore, the condition in the optimal range can be seen to improve the mechanical property of the enzyme synthesized nano-cellulose/PHBV composite material product.
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Claims (7)
1. An enzyme-synthesized nano-cellulose/PHBV composite material and a preparation method thereof, which comprises the following steps:
after the raw materials of the enzyme-synthesized nano-cellulose and PHBV are dried in vacuum, the raw materials are added into an injection molding device for injection molding to obtain an enzyme-synthesized nano-cellulose/PHBV composite material product with high mechanical property;
the enzyme synthesized nano-cellulose is prepared by glucose or cellobiose through the catalysis of cellodextrin phosphorylase;
the weight average molecular weight of the PHBV raw material is 10000-700000, and the HV content is 1-40%;
the content of the enzyme synthesized nano-cellulose in the composite material product in PHBV is 0.1-8 wt%.
2. The enzyme-synthesized nano-cellulose/PHBV composite material and the preparation method thereof according to claim 1, wherein the temperature of the screw for injection molding processing is 170-200 ℃.
3. The enzyme-synthesized nano-cellulose/PHBV composite material and the preparation method thereof according to claim 1, wherein the rotation speed of the screw for injection molding processing is 50-150 r/min.
4. The enzyme-synthesized nano-cellulose/PHBV composite material and the preparation method thereof according to claim 1, wherein the temperature of the material passing through the nozzle for injection molding is 170-200 ℃, the injection pressure is 150-300MPa, the pressure-maintaining pressure is 100-200MPa, the pressure-maintaining time is 10-100s, and the mold temperature is 50-70 ℃.
5. The enzyme-synthesized nano-cellulose/PHBV composite material and the preparation method thereof according to claim 1, wherein the enzyme-synthesized nano-cellulose is prepared by cellobiose molecules through the catalysis of cellodextrin phosphorylase.
6. The enzyme-synthesized nanocellulose/PHBV composite material and the preparation method thereof as claimed in claim 1, wherein the weight average molecular weight of the PHBV raw material is 20000-500000, and the HV content is 1% -25%.
7. The enzyme-synthesized nano-cellulose/PHBV composite material and the preparation method thereof according to claim 1, wherein the content of the enzyme-synthesized nano-cellulose in PHBV is 0.5 wt% -5 wt%.
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| CN114921071A (en) * | 2022-03-13 | 2022-08-19 | 宁波大学 | Antibacterial nanocellulose/PHBV composite material and preparation method thereof |
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