CN102268180A - Biobased degradable composite material and preparation method thereof - Google Patents
Biobased degradable composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biobased degradable composite material, which is a mixture of bamboo fibers and poly(hydroxybutyrate-hydroxyvalerate). Each 100 mass parts of the biobased degradable composite material comprises the following components in part by mass: 20 to 80 parts of bamboo fibers and 80 to 20 parts of poly(hydroxybutyrate-hydroxyvalerate). The invention also provides the preparation method of the biobased degradable composite material. The preparation process of the invention is simple, convenient and easy to implement, has high production efficiency, can lower cost, is clean and free from pollution and can improve the performance of the composite material.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of bio-based degradable composite material and preparation method thereof.
Background technology
Traditional fiber-reinforced resin matrix compound material mainly strengthens body, petroleum base thermoset or thermal plastic high polymer as resin matrix by conducts such as glass fibre, carbon fibers, obtains widespread use in the national economy every field.Because oil is Nonrenewable resources, day by day exhausted, for the Sustainable development of conventional composite materials brings great crises.In addition, the production of glass fibre, carbon fiber etc. not only expends the great number energy, and the carbon emission amount is huge, thermosetting resin curing process also discharges lot of V OC, threaten workers ' health and environment, the waste of conventional composite materials is difficult for degraded usually or reclaims, for ecotope brings heavy burden.For solving above-mentioned a series of problem, people press for that development is raw material, preparation process cleanliness without any pollution with the renewable resources, waste is recyclable or the degradable environmental-friendly matrix material.
Application number is that to disclose a kind of be the compound package material of main raw material with vegetable fibre and composite adhesive for 95117975.6 Chinese invention patent application, though have biodegradability preferably, but the prescription of composite adhesive and production process thereof are all very complicated, and the finished product fastness is not enough.
The patent No. is that to disclose a kind of be the degradeable plastic and plant composite material of main raw material with plant powder and composite adhesive for 97109168.4 Chinese invention patent, but need to use petroleum-based polypropylene, melamine resin, destroyed the full bio-based characteristic of this matrix material.
Application number is that to disclose a kind of be that resin matrix, vegetable fibre are the biodegradable composite that strengthens body with the poly(lactic acid) for 200710019693.9 Chinese invention patent application, this matrix material melt extrudes to make by forcing machine expects to make, because the higher melt viscosity of poly(lactic acid), and the melt viscosity that the interpolation fiber causes further rises, the length of the fiber that is added is lacked (less than 30mm), the content of fiber also lower (less than 50 parts), therefore limited to the reinforced effects of resin matrix.
Application number is the natural fibre reinforced polylactic acid polymer matrix composites that 200810041435.5 Chinese invention patent application discloses a kind of fully biodegradable, by modified natural fiber and poly(lactic acid) thin plate are alternately placed compression molding then.The length range broad of natural fiber (length-to-diameter ratio is 5～100), content also higher (the highest 80 parts), but, need before the preparation matrix material, carry out surface modification to natural fiber because the affinity of poly(lactic acid) and natural fiber is poor.Nonetheless, because poly(lactic acid) has higher melt viscosity, its wetting capacity to natural fiber is still relatively poor, thus the mechanical property of matrix material especially shock resistance is relatively poor.
Application number is that 200810163797.1 Chinese invention patent application discloses a kind of sound insulation composite material of bamboo fibrofelt and polypropylene and preparation method thereof, owing to adopt bamboo fiber felt and polypropylene powder to carry out compound, improved the content (50～70wt%) of bamboo fibers, but polypropylene is neither bio-based resin, can not biological degradation, and because melt polypropylene viscosity height, poor to the wetting capacity of bamboo fibers, need when the preparation matrix material, add softening agent, be unfavorable for the raising of composite product performance and quality stability.
Obviously, people have recognized that with natural fiber and bio-based degradable resin be the significance and importance that main raw material prepares the environmental type matrix material.But often not as glass fibre, carbon fiber, and the bio-based degradable resin also exists inherent chemical physics defective as easily degraded under at comparatively high temps, toughness and impact resistance difference etc. to natural fiber on performance.Therefore, the key of development natural fiber enhancing bio-based degradable resin based composites is to improve its performance.
As everyone knows, the performance of fiber-reinforced resin matrix compound material depend primarily on fortifying fibre character and and resin matrix between bonding force.In view of the performance of natural fiber own is difficult to further raising, thereby increase its length-to-diameter ratio and content just becomes inevitable choice.In addition, improving the bio-based degradable resin also is one of effective way that improves composite property to the wetting capacity of natural fiber.With regard to present known technology, as application number is that 95117975.6 the Chinese invention patent application and the patent No. are that 97109168.4 Chinese invention patent is disclosed, when resin system is the very low composite adhesive of viscosity, can improve the length-to-diameter ratio of natural fiber and content and the unlikely composite material forming problem that causes, but the preparation of composite adhesive and the production process of matrix material are all comparatively complicated, in the tackiness agent solidification process, also VOC be can discharge, workers ' health and cleaner production are unfavorable for; As application number is that 200710019693.9 Chinese invention patent application is disclosed, when resin system is biological base degradable polyphosphazene polymer lactic acid, because polylactic acid melt viscosity height, the length of requirement vegetable fibre is short when using forcing machine to carry out melt blending and making material, addition is lower, thereby has limited giving full play to of fiber reinforcement effect; As application number is that 200810041435.5 Chinese invention patent application and application number are that 200810163797.1 Chinese invention patent application is disclosed, adopt poly(lactic acid) thin plate or polypropylene powder as resin system, avoid in mixing process, using forcing machine, thereby increase the length-to-diameter ratio and the content of natural fiber, but because poly(lactic acid) and polyacrylic melt viscosity are all higher, be difficult to realize good immersional wetting, therefore still be unfavorable for the raising of composite property and quality stability fiber.In sum, bio-based degradable composite material by the preparation of present known method all exists prescription and production process complexity, production process release VOC, fiber length-to-diameter ratio to some extent and content is low or resin melt viscosity height, to problems such as fiber wetting capacity differences, demand development of new bio-based degradable composite material kind urgently and improve production technology to improve composite property, to reduce production costs, satisfy service requirements.
Summary of the invention
Lower for the production process complexity, the production efficiency that overcome prior biological base degradable matrix material, production cost is high, contaminate environment, the relatively poor deficiency of composite property, the invention provides that a kind of preparation process is simple and easy to do, production efficiency is high and reduce cost, the bio-based degradable composite material of cleanliness without any pollution, lifting composite property and preparation method thereof.
Adopt following technical scheme in order to solve the problems of the technologies described above:
A kind of bio-based degradable composite material, described bio-based degradable composite material are the mixture of bamboo fibers and polyhydroxybutyrate valeric acid copolyesters (PHBV), and mass fraction is that the mass fraction of each component is in 100 parts the bio-based degradable composite material:
20～80 parts of bamboo fiberss
80～20 parts of polyhydroxybutyrate valeric acid copolyesters (PHBV).
Preferably, described bamboo fibers length-to-diameter ratio is 100～2000;
Optionally, described polyhydroxybutyrate valeric acid copolyesters (PHBV) weight-average molecular weight is 15～750,000, and the molar content of hydroxyl valerate wherein (HV) is 1-45%.
A kind of preparation method of bio-based degradable composite material said method comprising the steps of: (1) passes through vacuum-drying respectively with bamboo fibers in the aforementioned bio-based degradable composite material component and polyhydroxybutyrate valeric acid copolyesters (PHBV); (2) dried bamboo fibers being made density through air method or combing method is 0.06～0.3g/cm
3Bamboo fiber felt; (3) by the electrostatic adhesion method with dried polyhydroxybutyrate valeric acid copolyesters (PHBV) powder and bamboo fiber felt in the ratio uniform mixing in the aforementioned bio-based degradable composite material component; (4) mixed polyhydroxybutyrate valeric acid copolyesters (PHBV) powder and bamboo fiber felt being placed temperature is that 172～195 ℃, pressure are to make the bio-based degradable composite material in the mould of 0.5～2.5MPa in hot-forming 1～5 minute.
Preferably, described bamboo fibers length-to-diameter ratio is 100～2000;
Optionally, described polyhydroxybutyrate valeric acid copolyesters (PHBV) weight-average molecular weight is 15～750,000, and the molar content of hydroxyl valerate wherein (HV) is 1-45%.
The invention has the advantages that: bio-based degradable composite material disclosed in this invention adopts abundant, with low cost bamboo fibers in source and the complete degradable polyhydroxybutyrate valeric acid of bio-based copolyesters (PHBV) as raw material, simple and easy to do, the cleanliness without any pollution of its preparation process.Because the PHBV resin is initially synthetic to be Powdered, is convenient to realize by the electrostatic adhesion method uniform mixing of bamboo fibers and PHBV, thereby avoids using any liquid dispersion medium.In addition, PHBV melt viscosity in composite material forming temperature range (172～194 ℃) is low, when bamboo fibers length-to-diameter ratio and content are higher, also can fast and effeciently soak into bamboo fibers, performance of composites is significantly improved, and shortened the shaping cycle of matrix material greatly, enhance productivity and reduce cost.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention and effect are further described.
Embodiment 1:
A kind of bio-based degradable composite material, this bio-based degradable composite material are the mixture of bamboo fibers and polyhydroxybutyrate valeric acid copolyesters, and mass fraction is that the mass fraction of each component is in 100 parts the bio-based degradable composite material:
20 parts of bamboo fiberss
80 parts of polyhydroxybutyrate valeric acid copolyesters (PHBV).
The length-to-diameter ratio of described bamboo fibers is 100～2000.The weight-average molecular weight of described polyhydroxybutyrate valeric acid copolyesters (PHBV) is 15～750,000, and the molar content of hydroxyl valerate wherein (HV) is 1-45%.
In the present embodiment, get length-to-diameter ratio and be 1050 bamboo fibers and weight-average molecular weight and be 150,000, hydroxyl valerate (HV) molar content is 45% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder.
Embodiment 2:
In the present embodiment, 50 parts of bamboo fiberss; 50 parts of polyhydroxybutyrate valeric acid copolyesters (PHBV).
Get length-to-diameter ratio and be 100 bamboo fibers and weight-average molecular weight and be 750,000, hydroxyl valerate (HV) molar content is 23% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 3:
In the present embodiment, 80 parts of bamboo fiberss; 20 parts of polyhydroxybutyrate valeric acid copolyesters (PHBV).
Get length-to-diameter ratio and be 2000 bamboo fibers and weight-average molecular weight and be 450,000, hydroxyl valerate (HV) molar content is 1% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 4:
Get length-to-diameter ratio and be 1050 bamboo fibers and weight-average molecular weight and be 150,000, hydroxyl valerate (HV) molar content is that 45% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder carries out vacuum-drying, the bamboo fibers drying temperature is 120 ± 5 ℃, the PHBV drying temperature is 60 ± 5 ℃, be 16 hours time of drying, and vacuum tightness is 100Pa; Getting dried bamboo fibers, to make density through combing method for 50 kilograms be 0.18g/cm
3Bamboo fiber felt; Get dried PHBV powder and pass through electrostatic adhesion method and bamboo fiber felt uniform mixing for 50 kilograms; Mixed PHBV powder and bamboo fiber felt being placed temperature is that 172 ℃, pressure are to make the bio-based degradable composite material in the mould of 0.5MPa in hot-forming 1 minute again.The socle girder notched Izod impact strength that records this matrix material is 6.6kJ/m
2, flexural strength is 27MPa, modulus in flexure is 2600MPa, in the test process in the matrix material fiber combine closely with resin matrix, demixing phenomenon does not take place.
Embodiment 5:
Get length-to-diameter ratio and be 100 bamboo fibers and weight-average molecular weight and be 750,000, hydroxyl valerate (HV) molar content is that 23% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder carries out vacuum-drying, the bamboo fibers drying temperature is 120 ± 5 ℃, the PHBV drying temperature is 60 ± 5 ℃, be 16 hours time of drying, and vacuum tightness is 100Pa; Getting dried bamboo fibers, to make density through the air method for 80 kilograms be 0.3g/cm
3Bamboo fiber felt; Get dried PHBV powder and pass through electrostatic adhesion method and bamboo fiber felt uniform mixing for 20 kilograms; Mixed PHBV powder and bamboo fiber felt being placed temperature is that 194 ℃, pressure are to make the bio-based degradable composite material in the mould of 2.5MPa in hot-forming 3 minutes again.The socle girder notched Izod impact strength that records this matrix material is 5.2kJ/m
2, flexural strength is 23MPa, modulus in flexure is 2900MPa, in the test process in the matrix material fiber combine closely with resin matrix, demixing phenomenon does not take place.
Embodiment 6:
Get length-to-diameter ratio and be 2000 bamboo fibers and weight-average molecular weight and be 450,000, hydroxyl valerate (HV) molar content is that 1% polyhydroxybutyrate valeric acid copolyesters (PHBV) powder carries out vacuum-drying, the bamboo fibers drying temperature is 120 ± 5 ℃, the PHBV drying temperature is 60 ± 5 ℃, be 16 hours time of drying, and vacuum tightness is 100Pa; Getting dried bamboo fibers, to make density through the air method for 20 kilograms be 0.06g/cm
3Bamboo fiber felt; Get dried PHBV powder and pass through electrostatic adhesion method and bamboo fiber felt uniform mixing for 80 kilograms; Mixed PHBV powder and bamboo fiber felt being placed temperature is that 183 ℃, pressure are to make the bio-based degradable composite material in the mould of 1.5MPa in hot-forming 5 minutes again.The socle girder notched Izod impact strength that records this matrix material is 5.7kJ/m
2, flexural strength is 25MPa, modulus in flexure is 2200MPa, in the test process in the matrix material fiber combine closely with resin matrix, demixing phenomenon does not take place.
Claims (6)
1. bio-based degradable composite material, it is characterized in that: this bio-based degradable composite material is the mixture of bamboo fibers and polyhydroxybutyrate valeric acid copolyesters, mass fraction is that the mass fraction of each component is in 100 parts the bio-based degradable composite material:
20～80 parts of bamboo fiberss
80～20 parts of polyhydroxybutyrate valeric acid copolyesters (PHBV).
2. bio-based degradable composite material as claimed in claim 1 is characterized in that: the length-to-diameter ratio of described bamboo fibers is 100～2000.
3. bio-based degradable composite material as claimed in claim 1 or 2 is characterized in that: the weight-average molecular weight of described polyhydroxybutyrate valeric acid copolyesters is 15～750,000, and the molar content of hydroxyl valerate wherein is 1-45%.
4. the preparation method of a bio-based degradable composite material as claimed in claim 1, it is characterized in that: this method may further comprise the steps: (1) passes through vacuum-drying respectively with bamboo fibers and polyhydroxybutyrate valeric acid copolyesters; (2) dried bamboo fibers being made density through air method or combing method is 0.06～0.3g/cm
3Bamboo fiber felt; (3) by the electrostatic adhesion method with dried polyhydroxybutyrate valeric acid copolyesters powder and bamboo fiber felt uniform mixing in proportion; (4) mixed polyhydroxybutyrate valeric acid copolyesters powder and bamboo fiber felt being placed temperature is that 172～195 ℃, pressure are to make the bio-based degradable composite material in the mould of 0.5～2.5MPa in hot-forming 1～5 minute;
Mass fraction is that the mass fraction of each component is in 100 parts the compound:
20～80 parts of bamboo fiberss
80～20 parts of polyhydroxybutyrate valeric acid copolyesters.
5. the preparation method of bio-based degradable composite material as claimed in claim 4 is characterized in that: the length-to-diameter ratio of described bamboo fibers is 100～2000.
6. as the preparation method of claim 4 or 5 described bio-based degradable composite materials, it is characterized in that: the weight-average molecular weight of described polyhydroxybutyrate valeric acid copolyesters is 15～750,000, and the molar content of hydroxyl valerate wherein is 1-45%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976486A (en) * | 2012-12-05 | 2013-03-20 | 宁波天安生物材料有限公司 | Material for water treatment |
| CN103011398A (en) * | 2012-12-13 | 2013-04-03 | 清华大学 | Method for removing nitrate nitrogen in water by using blended material including PHBV (Polyhydroxylbutyrate Valerate) and bamboo powder |
| CN103923445A (en) * | 2014-03-11 | 2014-07-16 | 绍兴文理学院 | Biodegradable natural bamboo fiber reinforced composite material |
| CN103937180A (en) * | 2014-03-11 | 2014-07-23 | 绍兴文理学院 | Preparation method for biodegradable raw bamboo fiber reinforced composite |
| CN103992626A (en) * | 2014-03-11 | 2014-08-20 | 郭筱洁 | Polyhydroxybutyrate valerate polyester composite material |
| CN106693520A (en) * | 2016-12-13 | 2017-05-24 | 厦门建霖工业有限公司 | Biodegradable active carbon fiber filtering core and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403134A (en) * | 2014-12-31 | 2015-03-11 | 桂林理工大学 | Preparation method of bio-based composite material |
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| CN101602882A (en) * | 2008-06-13 | 2009-12-16 | 中国科学院宁波材料技术与工程研究所 | Bamboo powder filled biomass-based resin composite material and preparation method thereof |
Non-Patent Citations (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976486A (en) * | 2012-12-05 | 2013-03-20 | 宁波天安生物材料有限公司 | Material for water treatment |
| CN102976486B (en) * | 2012-12-05 | 2014-04-16 | 宁波天安生物材料有限公司 | Material for water treatment |
| CN103011398A (en) * | 2012-12-13 | 2013-04-03 | 清华大学 | Method for removing nitrate nitrogen in water by using blended material including PHBV (Polyhydroxylbutyrate Valerate) and bamboo powder |
| CN103011398B (en) * | 2012-12-13 | 2013-12-04 | 清华大学 | Method for removing nitrate nitrogen in water by using blended material including PHBV (Polyhydroxylbutyrate Valerate) and bamboo powder |
| CN103923445A (en) * | 2014-03-11 | 2014-07-16 | 绍兴文理学院 | Biodegradable natural bamboo fiber reinforced composite material |
| CN103937180A (en) * | 2014-03-11 | 2014-07-23 | 绍兴文理学院 | Preparation method for biodegradable raw bamboo fiber reinforced composite |
| CN103992626A (en) * | 2014-03-11 | 2014-08-20 | 郭筱洁 | Polyhydroxybutyrate valerate polyester composite material |
| CN106693520A (en) * | 2016-12-13 | 2017-05-24 | 厦门建霖工业有限公司 | Biodegradable active carbon fiber filtering core and preparation method thereof |
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| CN102268180B (en) | 2012-11-14 |
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Application publication date: 20111207 Assignee: Hangzhou craftwork Co., Ltd. Assignor: Zhejiang Academy of Forestry Contract record no.: 2018330000017 Denomination of invention: Biobased degradable composite material and preparation method thereof Granted publication date: 20121114 License type: Common License Record date: 20180305 Application publication date: 20111207 Assignee: Shaoxing Yongsheng New Material Co., Ltd. Assignor: Zhejiang Academy of Forestry Contract record no.: 2018330000016 Denomination of invention: Biobased degradable composite material and preparation method thereof Granted publication date: 20121114 License type: Common License Record date: 20180305 Application publication date: 20111207 Assignee: Shaoxing Shangyu Yu Yu Plastic Electrical Appliance Co., Ltd. Assignor: Zhejiang Academy of Forestry Contract record no.: 2018330000014 Denomination of invention: Biobased degradable composite material and preparation method thereof Granted publication date: 20121114 License type: Common License Record date: 20180302 Application publication date: 20111207 Assignee: Xiapu Yutong molding plant, Beilun District, Ningbo Assignor: Zhejiang Academy of Forestry Contract record no.: 2018330000015 Denomination of invention: Biobased degradable composite material and preparation method thereof Granted publication date: 20121114 License type: Common License Record date: 20180302 |