CN108250696A - A kind of cellulose complete biodegradable construct blow-molded and preparation method thereof - Google Patents
A kind of cellulose complete biodegradable construct blow-molded and preparation method thereof Download PDFInfo
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- CN108250696A CN108250696A CN201711461268.5A CN201711461268A CN108250696A CN 108250696 A CN108250696 A CN 108250696A CN 201711461268 A CN201711461268 A CN 201711461268A CN 108250696 A CN108250696 A CN 108250696A
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- Prior art keywords
- cellulose
- complete biodegradable
- molded
- construct blow
- compatilizer
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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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a kind of cellulose complete biodegradable construct blow-molded and preparation method thereof, the raw material for preparing of the material includes：Poly terephthalic acid adipic acid fourth diester, polylactic acid, polyvinyl alcohol, straw powder, compatilizer, additive and nano redigity organic material；Wherein, compatilizer is at least one of polyethylene glycol, silane coupling agent, Al-Ti-diffused steel and titanate esters；Additive is one or more of plasticizer, crosslinking agent and in-lubricant；Nano redigity organic material is Cellulose nanocrystal body or cellulose nanometer fibril.Preparation method is that compatilizer is made into ethanol solution, is uniformly sprayed in the mixture of straw powder and nano redigity organic material, is dried after being placed at room temperature for, and it is uniform to add surplus stock stirring and mixing, adds in double screw extruder and is kneaded, and is granulated.The plastic product mechanical property of the present invention improves, and degradability is good, environment friendly and pollution-free.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of cellulose complete biodegradable construct blow-molded and its preparation
Method.
Background technology
Plastic product since the advent of the world brings great convenience with its versatility and practicability to the work and life of people,
It is commonly used in the almost all of field of production, life, scientific research etc..And the growth of plastic package material in the world market
Rate and significantly larger than other application field.China is one of ten big plastic products production and consumption states in the world, is packed for plastics
It is most of in the form of waste film, agricultural mulching and polybag, be dropped in the environment, it is difficult to degrade and ecological environment is made
Into potential hazard.
Biological degradation plastics be it is a kind of have excellent performance, it is discarded after can completely be decomposed by environmental microorganism,
Finally by inorganization as the high molecular material of a component part of Carbon cycle in nature.
Rice straw is a kind of gramineae plant, is the most important agricultural byproduct in the whole world, while is also that utility value is most in the world
High agricultural product (187,000,000,000 U.S. dollar of global economic impact in 2011).For a long time, agricultural crop straw is mainly used as fertilizer, combustion
Material, feed and paper making raw material, utilization rate is less than 50%.Remaining major part stalk all does burning disposal, results in serious haze
And other air pollutions.
The source of nano-cellulose is very extensive, and with high-crystallinity, low-density, high Young's modulus, high intensity, high ratio
Surface area, low thermal coefficient of expansion, hydrophily, hyperfine structure, life are without degradable, biocompatibility and recyclability.
However stalk biological degradation plastics of the prior art in preparation process since the modified effect to stalk has
It limits, has in the biological degradation plastics mechanical property produced with conventional plastic or even with pure biological degradation plastics larger
Gap can not meet requirement used in everyday.And due to the particularity of blow molding process, even if causing to be molded, but appearance
It can not meet the requirements, it is impossible to accomplish practical really application.
Invention content
In order to solve the above problem of the prior art, the present invention provides a kind of cellulose complete biodegradables to be blow molded material
Material.
The cellulose complete biodegradable construct blow-molded, by mass percentage, prepares raw material and includes：
Wherein, the compatilizer is one or more of polyethylene glycol, silane coupling agent, Al-Ti-diffused steel and titanate esters；
The additive is one or more of plasticizer, crosslinking agent and in-lubricant；The nano redigity organic material is fiber
Plain nanocrystal or cellulose nanometer fibril.
The source of nano-cellulose is very extensive, and with high-crystallinity, low-density, high Young's modulus, high intensity, high ratio
Surface area, low thermal coefficient of expansion, hydrophily, hyperfine structure, biodegradability, biocompatibility and recyclability.Fiber
Plain nanocrystal (cellulose nanocrystals, CNC), cellulose nanometer fibril (cellulose nanofiber,
CNF), diameter is in 5-20nm or so, and for the length of CNC between 50-300nm, CNF draw ratios are bigger, and length is generally up to micro-
Meter level.Nano redigity organic material source is very extensive, and a small amount of use has positive effect to the promotion of system mechanical property.
Preferably, the size of the nano redigity organic material is 1~100nm.
Preferably, the plasticizer is ethylene glycol, propylene glycol, glycerine, xylitol, mannitol or sorbierite.
Preferably, the crosslinking agent is maleic anhydride grafted polyethylene wax (Ma-g-PE), epoxy resin, epoxidized soybean oil
One or more of.
Preferably, the in-lubricant is one or more of polyethylene wax, polypropylene wax and atoleine.
Preferably, by mass percentage, raw material is：
It is found through overtesting, the cellulose complete biodegradable construct blow-molded that each ingredient of above-mentioned amount ranges is selected to prepare,
Thin film mechanical performance such as tensile strength, elongation at break, puncture strength and the tearing strength processed with it is more excellent.It is processed into
During final products, product surface is smooth, has excellent appearance.
The present invention also provides the preparation methods of the cellulose complete biodegradable construct blow-molded described in any of the above one, are
Compatilizer is made into ethanol solution, is uniformly sprayed in the mixture of straw powder and nano redigity organic material, after being placed at room temperature for
Drying, it is uniform to add surplus stock stirring and mixing at 60~130 DEG C, adds in double screw extruder, at 130~190 DEG C
It is kneaded, is granulated.
Preferably, in above-mentioned preparation method, it is 6 hours to be placed at room temperature for the time, and drying condition is 105 DEG C of dry 2h.
The invention has the advantages that：
1st, nano redigity organic material used in the present invention can significantly increase the mechanical property of composite material, and add
Dosage is small, easy to process.The biodegradable composite material produced is when following process is into final consumption product, properties of product
Superior, appearance is outstanding.
2nd, the present invention is used compatilizer wiring solution-forming, is uniformly sprayed to CNCs/ straw powders or CNFs/ straw powder mixing materials
On material, it ensure that CNCs or CNFs do not reunite, can uniformly disperse open, play the role of effectively promoting system mechanical property.
3rd, biological degradation plastics are blended using biodegradable straw powder in the present invention, can complete biodegradable after use
Cheng Shui and carbon dioxide, it is environmentally safe.
4th, plasticizer used in the present invention, compatilizer so that straw powder has thermoplasticity, can be processed so as to improve it
Performance and the compatibility with biological degradation plastics so that composite material has good performance and processing performance.
5th, additive used in the present invention is nontoxic, and is derived partly from biomass.
6th, straw powder used in the present invention belongs to agricultural wastes, and the processing mode of burning different from the past provides
A kind of utilization method of more economical environmental protection maximizes the utility value of stalk.
Specific embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be preferably
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment and comparative example, by by identical formula, to embody the different usages of comparison nano redigity organic material
The difference between the effects promoted to material property.
Embodiment：
(1) compatilizer is made into ethanol solution, be uniformly sprayed on the mixture containing CNCs or CNFs and straw powder, room temperature
6h is placed, then 105 DEG C of dry 2h, the mixing material after drying are spare；Add in biological degradation plastics, plasticizer, crosslinking agent,
In-lubricant, stirring and mixing is uniform at 60~130 DEG C；
(2) it is reacted in double screw extruder：The material that step (1) is obtained is added in double screw extruder, 130~
190 DEG C of mixings, are granulated to get to cellulose complete biodegradable construct blow-molded；
Raw material components see the table below：
The performance of embodiment cellulose complete biodegradable construct blow-molded is as follows：
Comparative example：
It using the formula of embodiment 1-4, is corresponding in turn to labeled as comparative example 1-4, preparation method is as follows：
(1) by CNCs or CNFs, plasticizer, crosslinking agent, in-lubricant, compatilizer, biological degradation plastics and straw powder
It is put into high-speed mixer, high-speed stirred is mixed evenly at 60~130 DEG C；
(2) it is reacted in double screw extruder：The material that step (1) is obtained is added in double screw extruder, 130~
190 DEG C of mixings, are granulated to get to cellulose complete biodegradable construct blow-molded.
The performance of comparative fibers element complete biodegradable construct blow-molded is as follows：
The experimental results showed that cellulose complete biodegradable construct blow-molded formula of the invention improve after mechanical property have it is larger
It improves, ethanol solution is in addition made into using compatilizer, is first uniformly sprayed to the mixture upper chamber containing CNCs or CNFs and straw powder
Temperature places the pretreatment mode of re-dry, can further improve product mechanical property.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.The equivalent substitute or transformation that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is subject to claims.
Claims (8)
1. a kind of cellulose complete biodegradable construct blow-molded, which is characterized in that by mass percentage, prepare raw material and include：
Wherein, the compatilizer is one or more of polyethylene glycol, silane coupling agent, Al-Ti-diffused steel and titanate esters；It is described
Additive is one or more of plasticizer, crosslinking agent and in-lubricant；The nano redigity organic material is received for cellulose
Meter Jing Ti or cellulose nanometer fibril.
2. cellulose complete biodegradable construct blow-molded according to claim 1, which is characterized in that the nano redigity is organic
The size of material is 1~100nm.
3. cellulose complete biodegradable construct blow-molded according to claim 1, which is characterized in that the plasticizer is second two
Alcohol, propylene glycol, glycerine, xylitol, mannitol or sorbierite.
4. cellulose complete biodegradable construct blow-molded according to claim 1, which is characterized in that the crosslinking agent is Malaysia
One or more of anhydride grafted lldpe wax, epoxy resin, epoxidized soybean oil.
5. cellulose complete biodegradable construct blow-molded according to claim 1, which is characterized in that the in-lubricant is poly-
One or more of ethylene waxes, polypropylene wax and atoleine.
6. cellulose complete biodegradable construct blow-molded according to claim 1, which is characterized in that by mass percentage,
Raw material is：
7. the preparation method of the cellulose complete biodegradable construct blow-molded described in claim 1~6 any one, feature exist
In compatilizer is made into ethanol solution, is uniformly sprayed in the mixture of straw powder and nano redigity organic material, is placed at room temperature for
After dry, it is uniform to add surplus stock stirring and mixing at 60~130 DEG C, adds in double screw extruder, 130~190
DEG C be kneaded, be granulated.
8. the preparation method of nano redigity organic material enhancing biology base stalk composite plastic according to claim 7,
It is characterized in that, it is 6 hours to be placed at room temperature for the time, and drying condition is 105 DEG C of dry 2h.
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| CN201711461268.5A CN108250696A (en) | 2017-12-28 | 2017-12-28 | A kind of cellulose complete biodegradable construct blow-molded and preparation method thereof |
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| CN201711461268.5A CN108250696A (en) | 2017-12-28 | 2017-12-28 | A kind of cellulose complete biodegradable construct blow-molded and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423737A (en) * | 2020-05-08 | 2020-07-17 | 深圳国至新材料科技有限公司 | Bio-based degradable lunch box material and preparation method thereof |
| CN111925631A (en) * | 2020-07-31 | 2020-11-13 | 华南理工大学 | Nano cellulose cellosilk/PBAT film and preparation method and application thereof |
| CN112300542A (en) * | 2019-07-29 | 2021-02-02 | 罗惠民 | Nanoscale plant fiber modified biodegradable composite material and preparation method and application thereof |
| CN112442261A (en) * | 2019-09-04 | 2021-03-05 | 凯麦特科技(深圳)有限公司 | Antibacterial biodegradable composite material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300542A (en) * | 2019-07-29 | 2021-02-02 | 罗惠民 | Nanoscale plant fiber modified biodegradable composite material and preparation method and application thereof |
| CN112442261A (en) * | 2019-09-04 | 2021-03-05 | 凯麦特科技(深圳)有限公司 | Antibacterial biodegradable composite material and preparation method and application thereof |
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| CN111925631A (en) * | 2020-07-31 | 2020-11-13 | 华南理工大学 | Nano cellulose cellosilk/PBAT film and preparation method and application thereof |
| CN111925631B (en) * | 2020-07-31 | 2023-06-20 | 华南理工大学 | Nanocellulose fibril/PBAT film and preparation method and application thereof |
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