CN103012857A - Microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and preparation method thereof - Google Patents
Microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and preparation method thereof Download PDFInfo
- Publication number
- CN103012857A CN103012857A CN2012105168264A CN201210516826A CN103012857A CN 103012857 A CN103012857 A CN 103012857A CN 2012105168264 A CN2012105168264 A CN 2012105168264A CN 201210516826 A CN201210516826 A CN 201210516826A CN 103012857 A CN103012857 A CN 103012857A
- Authority
- CN
- China
- Prior art keywords
- starch
- microcrystalline cellulose
- polycaprolactone
- coupling agent
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and a preparation method thereof. The microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material comprises the following components in parts by weight: 100 (as a base number) of starch, 0.1-10 of microcrystalline cellulose, 1-100 of polycaprolactone, 0.1-10 of coupling agent, and 10-50 of glycerol. The preparation method comprises the steps: dispersing microcrystalline cellulose; refining the starch; drying polycaprolactone; evenly mixing microcrystalline cellulose and the refined starch; evenly mixing microcrystalline cellulose and the refined starch, polycaprolactone and the coupling agent; and pelletizing to obtain granules. The starch-based blending material reinforced by microcrystalline cellulose and polycaprolactone is tripled obviously in tensile strength, has excellent mechanical property and full-biodegradation property, is simple in raw materials, and convenient to prepare, and can be used for producing various materials and be widely applied in the field of degradable plastics.
Description
Technical field
The present invention relates to a kind of starch base complete biodegradable intermingling material that strengthens based on Microcrystalline Cellulose and polycaprolactone and preparation method thereof.
Background technology
In recent years, global environment and resource problem have caused the plastic material take oil as the source to enjoy challenge, and degradable high polymer material receives much concern because of its degradability environmentally safe.Wherein, starch is a class important in the natural polymer, because of its environmental friendliness, renewable, research that the characteristics such as the source is abundant, low price extensively are used to plastic material, become study hotspot [the Chiellini E. in the degradable plastics, Solaro R. Biodegradable polymeric materials. Advanced Materials, 1996,8 (4): 305-313.].Yet the molecular structure characteristics of starch itself have caused the infeasibility of its straight forming processing, therefore need to add corresponding fluidizer and improve its workability with raising.But fluidizer generally is small molecules, and it joins the reduction that will cause the starch material mechanical property in the starch.Therefore, solve the processibility of starch material and the contradiction between the mechanical property, must guarantee further to improve its mechanical property under the prerequisite that starch material can be processed.Usually, polymer by adopt adding synthetic class or the method for toughener can improve mechanical property [the Tang X. of starch-based material, Alavi S. Recent advances in starch, polyvinyl alcohol based polymer blends, nanocomposites and their biodegradability. Carbohydrate Polymers, 2011,85 (1): 7-16.].Wherein, polycaprolactone is the biodegradable synthetic family macromolecule of a class, has excellent mechanical property when using as plastic material, is the good biodegradable polymer toughener of a class therefore.The intermingling material of polycaprolactone and starch has correlative study, but the polycaprolactone that needs to add more amount just can make starch-based material reach preferably mechanical property, and the adding of more amount polycaprolactone will cause the significantly raising of starch-based material production cost.Although being used for starch-based material, some other toughener can improve its mechanical property [Vertuccio L., Gorrasi G., Sorrentino A., Vittoria V. Nano clay reinforced PCL/starch blends obtained by high energy ball milling. Carbohydrate Polymers, 2009,75 (1): 172-179.], but cost is still higher, and there are the shortcomings such as preparation process is complicated, mechanical property is relatively poor, degradable is difficult, greatly limited the widespread use of starch-based material.
Summary of the invention
A purpose of the present invention is to provide a kind of starch base complete biodegradable intermingling material based on Microcrystalline Cellulose and polycaprolactone enhancing.
Another object of the present invention is to provide a kind of preparation method of the starch base complete biodegradable intermingling material that strengthens based on Microcrystalline Cellulose and polycaprolactone.
Starch base complete biodegradable intermingling material based on Microcrystalline Cellulose and polycaprolactone enhancing of the present invention, its component comprises: Microcrystalline Cellulose, polycaprolactone, coupling agent, starch, glycerine etc.
Wherein, the structural formula of the Microcrystalline Cellulose described in the present invention is:
N is the polymerization degree of Microcrystalline Cellulose, and the n value is: 20 ~ 5000;
The structural formula of the polycaprolactone described in the present invention:
M is the polymerization degree of polycaprolactone, and the m value is: 100 ~ 5000;
Coupling agent described in the present invention is a kind of in silane coupling agent or the titanate coupling agent, wherein: silane coupling agent comprises KH550, KH560, KH570, KH792, DL602, DL171 etc., and titanate coupling agent comprises NDZ-101, NDZ-102, NDZ-105, NDZ-130, NDZ-201 etc.
Starch described in the present invention is a kind of in native starch or the modified starch, wherein: native starch comprises potato starch, W-Gum, wheat starch, rice starch, legume starch etc., modified starch bag pre-gelatinized starch, dextrin, denaturated starch by acid, etherification starch, esterification starch etc.
The starch base complete biodegradable intermingling material that strengthens based on Microcrystalline Cellulose and polycaprolactone of the present invention, its component concentration is: in parts by weight, take 100 parts of starch as radix, Microcrystalline Cellulose 0.1 ~ 10, polycaprolactone 1 ~ 100, coupling agent 0.1 ~ 10, glycerine 10 ~ 50.
The preparation method of the starch base complete biodegradable intermingling material that strengthens based on Microcrystalline Cellulose and polycaprolactone of the present invention may further comprise the steps:
(1) Microcrystalline Cellulose is dispersed in the glycerine, the ultrasonic Microcrystalline Cellulose that makes is uniformly dispersed;
(2) starch is refined to is equal to or less than 400 orders;
(3) polycaprolactone is fully dry;
(4) step (1) is dispersed in Microcrystalline Cellulose in the glycerine and the starch of step (2) and sets high mixing in the fast mixing machine;
(5) material of step (4), material and the coupling agent of step (3) are set high mixing in the fast mixing machine;
(6) material of step (5) is put granulation is pellet in the twin screw extruder.
The component of Microcrystalline Cellulose, polycaprolactone and the coupling agent that strengthens for the starch base intermingling material of the present invention is simple, the effect that is used for enhancing starch base intermingling material is remarkable, resulting starch base intermingling material based on Microcrystalline Cellulose and polycaprolactone enhancing has excellent mechanical property, and feed composition is simple, preparation process is convenient, have complete biodegradable and lower cost, can make various materials (film, sheet material, sheet material etc.) and be widely used in the degradable plastics field, be conducive to the widespread use of starch-based material.
Embodiment
Embodiment 1:
(1) take by weighing 40 the gram Microcrystalline Celluloses, under agitation join 600 the gram glycerine in make its dispersion comparatively even.Then the mixed solution of this dispersion was put in the ultrasonic instrument ultrasonic 30 minutes, Microcrystalline Cellulose fully is uniformly dispersed.
(2) starch is placed ultrafine crusher be refined to 400 orders.
(3) taking by weighing 857 gram polycaprolactones places vacuum drying oven fully dry.
(4) take by weighing refinement starch 2000 grams that obtain in the step (2), set high fast mixing machine high speed mixing 10 minutes, then the Microcrystalline Cellulose that step (1) is dispersed in the glycerine joins in the high-speed mixer and refinement starch high-speed mixing 10 minutes with glycerol mixture, and it is for subsequent use after 1 day to mix rear taking-up mixture sealing and standing.
(5) material and the 40 gram silane coupling agent KH570 with the material after obtaining leaving standstill in the step (4), step (3) place high-speed mixer to mix together 10 minutes, and are fully evenly mixed.
(6) material that step (5) is obtained places the twin screw extruder granulation, namely obtains the starch base complete biodegradable pellet that Microcrystalline Cellulose and polycaprolactone strengthen.
The resulting starch base blend pellet based on Microcrystalline Cellulose and polycaprolactone enhancing of present embodiment is made batten through injection molding, tests its tensile property according to GB/T 1040.1-2006.Detect discovery by tensile property, the tensile strength of the purer plasticized starch of tensile strength of the starch base intermingling material after polycaprolactone strengthens has improved 107%, the tensile strength of the starch base intermingling material after further the tensile strength of the starch base intermingling material of process Microcrystalline Cellulose enhancing strengthens than polycaprolactone has further improved 50%, i.e. the tensile strength of the purer plasticized starch of starch base intermingling material of process Microcrystalline Cellulose and polycaprolactone enhancing has improved 211%.
?
Embodiment 2:
(1) take by weighing 80 the gram Microcrystalline Celluloses, under agitation add 600 the gram glycerine in make its dispersion comparatively even.Then the mixed solution of this dispersion was put in the ultrasonic instrument ultrasonic 30 minutes, Microcrystalline Cellulose fully is uniformly dispersed.
(2) starch is placed ultrafine crusher be refined to 400 orders.
(3) taking by weighing 500 gram polycaprolactones places vacuum drying oven fully dry.
(4) take by weighing refinement starch 2000 grams that obtain in the step (2), set high fast mixing machine high speed mixing 10 minutes, then the Microcrystalline Cellulose that step (1) is dispersed in the glycerine joins in the high-speed mixer and refinement starch high-speed mixing 10 minutes with glycerol mixture, and it is for subsequent use after 1 day to mix rear taking-up mixture sealing and standing.
(5) material and the 40 gram silane coupling agent KH570 with the material after obtaining leaving standstill in the step (4), step (3) place high-speed mixer to mix together 10 minutes, and are fully evenly mixed.
(6) material that step (5) is obtained places the twin screw extruder granulation, namely obtains the starch base complete biodegradable pellet that Microcrystalline Cellulose and polycaprolactone strengthen.
The resulting starch base blend pellet based on Microcrystalline Cellulose and polycaprolactone enhancing of present embodiment is made batten through injection molding, tests its tensile property according to GB/T 1040.1-2006.Detect discovery by tensile property, the tensile strength of the purer plasticized starch of tensile strength of the starch base intermingling material after polycaprolactone strengthens has improved 82%, the tensile strength of the starch base intermingling material after further the tensile strength of the starch base intermingling material of process Microcrystalline Cellulose enhancing strengthens than polycaprolactone has further improved 65%, i.e. the tensile strength of the purer plasticized starch of starch base intermingling material of process Microcrystalline Cellulose and polycaprolactone enhancing has improved 200%.
More than two embodiment proved that Microcrystalline Cellulose and polycaprolactone are a kind of tougheners of good starch-based material, have more excellent mechanical property and water tolerance preferably through the starch base intermingling material after strengthening, and feed composition is relatively simple, easy to prepare, have complete biodegradable and lower cost, can make various materials (film, sheet material, sheet material etc.) and be widely used in the degradable plastics field.
Claims (3)
1. the starch base complete biodegradable intermingling material based on Microcrystalline Cellulose and polycaprolactone enhancing is characterized in that this material component is: Microcrystalline Cellulose, polycaprolactone, coupling agent, starch, glycerine etc.
2. according to right 1 described starch base complete biodegradable intermingling material based on Microcrystalline Cellulose and polycaprolactone enhancing, it is characterized in that, this material component content is: in parts by weight, take 100 parts of starch as radix, Microcrystalline Cellulose 0.1 ~ 10, polycaprolactone 1 ~ 100, coupling agent 0.1 ~ 10, glycerine 10 ~ 50.
3. the preparation method of the starch base complete biodegradable intermingling material that strengthens according to right 1,2 described Microcrystalline Celluloses and polycaprolactone is characterized in that the method may further comprise the steps:
(1) Microcrystalline Cellulose is dispersed in the glycerine, the ultrasonic Microcrystalline Cellulose that makes is uniformly dispersed;
(2) starch is refined to is equal to or less than 400 orders;
(3) polycaprolactone is dry;
(4) step (1) is dispersed in Microcrystalline Cellulose in the glycerine and the refinement starch of step (2) and sets high mixing in the fast mixing machine;
(5) material of step (4), material and the coupling agent of step (3) are set high mixing in the fast mixing machine;
(6) material of step (5) is put granulation is pellet in the twin screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105168264A CN103012857A (en) | 2012-12-06 | 2012-12-06 | Microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105168264A CN103012857A (en) | 2012-12-06 | 2012-12-06 | Microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103012857A true CN103012857A (en) | 2013-04-03 |
Family
ID=47961993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105168264A Pending CN103012857A (en) | 2012-12-06 | 2012-12-06 | Microcrystalline cellulose and polycaprolactone reinforced starch-based full-biodegradable blending material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103012857A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115744A (en) * | 2016-06-22 | 2016-11-16 | 湖南工业大学 | A kind of ultra-fine NaHCO3particle and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524897A (en) * | 2003-02-25 | 2004-09-01 | Fully bio-degradable plastic master batch and preparing process thereof | |
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
-
2012
- 2012-12-06 CN CN2012105168264A patent/CN103012857A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524897A (en) * | 2003-02-25 | 2004-09-01 | Fully bio-degradable plastic master batch and preparing process thereof | |
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| L.AVEROUS, ET AL.: "Properties of thermoplastic blends: starch–polycaprolactone", 《POLYMER》 * |
| 陈志民等: "淀粉的改性及其在可降解塑料和橡胶中的应用研究", 《世界科技研究与发展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115744A (en) * | 2016-06-22 | 2016-11-16 | 湖南工业大学 | A kind of ultra-fine NaHCO3particle and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012856A (en) | Microcrystalline cellulose and polyvinyl alcohol reinforced starch-based full-biodegradable blending material and preparation method thereof | |
| CN102675804B (en) | Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof | |
| CN102634073B (en) | Starch/polypropylene degradable composite material and preparation method thereof | |
| CN103881340B (en) | A kind of preparation method of biomass fiber-aliphatic polyester composite material | |
| CN103289131A (en) | Preparation method for starch-polyvinyl alcohol biologically-cross-linked nano-composite plastic film | |
| CN103992517A (en) | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof | |
| CN102477216B (en) | Polybutylene succinate fully biodegradable material and preparation process thereof | |
| CN105440606A (en) | Preparation method of fully biodegradable starch/polylactic acid base resin | |
| CN108948690B (en) | Polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN102690488B (en) | Degradable starch-based plastic | |
| CN105504727B (en) | A kind of high tenacity fully-degradable polylactic acid based composites and preparation method thereof | |
| TW201336595A (en) | Thermoplastic starch composition derives from agricultural waste | |
| CN102702580A (en) | Full-biodegradable starch-base in-situ fiber reinforced composite material and preparation method thereof | |
| CN104893009A (en) | Starch-based composite and preparation method thereof | |
| CN104387621A (en) | Thermoplastic starch material and process for preparing same | |
| CN102321354A (en) | A kind of plasticizing polylactic acid/composite polyethylene material and preparation method thereof | |
| CN102134380B (en) | Completely biodegradable composite material and preparation method thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN101792539B (en) | Method for preparing full-starch full-biodegradable thermoplastic plastic | |
| CN104194288A (en) | Water bamboo shell fiber modified poly adipic acid/butylene terephthalate composite material and preparation method thereof | |
| CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
| CN101293994A (en) | Multi-component totally degradable polymer composite and its method preparation | |
| CN104804387B (en) | A kind of full bio-based degradable poly lactic acid composite and preparation method thereof | |
| CN111234484B (en) | Full-bio-based degradable polylactic acid/starch composite material and preparation method thereof | |
| CN103205023A (en) | Preparation method of bamboo powder/white carbon black composite reinforced starch-based degradable plastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130403 |