CN109824924A - A kind of packaging film and preparation method thereof that can be degradable - Google Patents
A kind of packaging film and preparation method thereof that can be degradable Download PDFInfo
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- CN109824924A CN109824924A CN201811603854.3A CN201811603854A CN109824924A CN 109824924 A CN109824924 A CN 109824924A CN 201811603854 A CN201811603854 A CN 201811603854A CN 109824924 A CN109824924 A CN 109824924A
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Abstract
The present invention provides a kind of packaging films and preparation method thereof that can be degradable, this method is using straw, and starch and degradation plastic material are raw material, is made by following steps: (1) by crushing to straw, alkali process, defibrination process obtain plant straw fibers slurry；(2) by modified to food starch, obtained thermoplastic starch；(3) above-mentioned plant straw fibers slurry and thermoplastic starch are blended with degradation plastic material, high temperature plasticizing.The beneficial effect is that packaging film of the invention can be degradable in nature, not can cause environmental pollution；Film component is safe and non-toxic, can be used for food packaging；The excellent in mechanical performance such as tensile strength, the elongation at break of film；Raw material sources are abundant, and production cost is low, enriches the resource utilization of stalk；Simple production process is controllable, and stability is good, is suitble to large-scale industrial production.
Description
Technical field
The invention belongs to plastic products technology fields, more particularly, to a kind of packaging film that can be degradable and its system
Preparation Method.
Background technique
Plastics are the important foundation materials of man invented, are brought great convenience to people's production and life.From 20
The 50's of century, global plastics annual growth are averagely maintained at 8.5%.By 2016, global plastics yield reached
3.35 hundred million tons.China is world's plastics-production and using big country, many of plastic product, such as polyvinyl chloride (PVC), amino mould
Plastics Isoquant has been positioned at global first place, and the potentiality further increased are still very huge.After these plastics uses, one
Partially due to not collected processing timely and effectively and entering environment, and broken, corruption occurs in the environment, gives earth's surface
Serious environmental pollution is brought in water, soil and ocean etc..
On the other hand, with the development of modern economy, the industries such as online shopping and take-away are grown rapidly, and one for packed and transported
The demand of secondary property plastic products is huge, and resource and environment face unprecedented pressure, wherein plastics rubbish of interest the most social
Rubbish source is plastics mess-tin, polybag and agriculture plastic film.Since 21 century, since petroleum resources are deficient and petroleum base
The research and development of the problem of environmental pollution that plastics cause, environmentally friendly biodegradable plastic become focus concerned by people.It is degradable
Plastics (BDP) are also known as environmental-friendly degradative plastics, have photodegradable plastics, biology drop using wide degradation plastic at present
Solve plastics, light/biodegradation plastic and complete degradable plastic.The development of degradation plastic produces the mankind from petroleum base is relied on
Plastics, plastics can also be produced using biology bases such as starch, cellulose, protein by developing to.It should say that degradation plastic is always
Policy support and encouragement, and the important branch of plastics-production development in recent years.
But in fact, there are higher cost, complex process, heat resistances for general biodegradation material compared with conventional plastic
More or less disadvantage such as difference, is not easy to promote.Some degradation plastics declared not are Wholly-degradable, when degradable portion
Divide after completing degradation, the remaining plastic flakes that cannot be degraded enter environment, it is more difficult to collect and handle, bring more serious ring
Border problem.
Summary of the invention
The present invention is directed to problem above, and providing one kind can be degradable, the preparation method of safe and non-toxic packaging film,
Described method includes following steps:
S1: by straw crushed after being dried, the NaOH water of 0.5 ~ 2mol/L is added by 3 ~ 5 times of quality of straw after crushing
Solution, and in 80 ~ 100 DEG C of 1 ~ 3h of closed processes, obtain processing feed liquid；
S2: after processing feed liquid described in step S1 is washed with water 2 ~ 3 times, defibrination process 3 ~ 5 times, mesh screen is then crossed, filtrate system is taken
Obtain plant straw fibers slurry；
S3: starch and organic solvent 1:1 ~ 3 in mass ratio are pre-mixed, then add the nontoxic increasing of 10 ~ 20% content of starch
Agent is moulded, under 60 ~ 90 DEG C of constant temperature, 1000 ~ 4000r/min at the uniform velocity stirs 2 ~ 3h, until being plasticized, sealing and standing 20 ~
For 24 hours, so that starch is fully absorbed solvent, preferably complete process of osmosis, finally obtain thermoplastic starch；
S4: it plasticates: by thermoplastic starch described in plant straw fibers slurry described in step S2 and step S3 while being added to pre-
In the degradation plastic first melted, 150 ~ 200 DEG C of temperature stir 30 ~ 50 min with the speed of 40 ~ 60r/min, then take out modeling
Material after refining, calendering or film extrusion, wherein plant straw fibers slurry account for thermoplastic starch mass percent be 5 ~
15%, the weight of thermoplastic starch is 5 ~ 10 times of degradation plastic.
Further, the straw is one of corn stover, rice straw or broomcorn straw or a variety of.
Straw is a kind of Biomass Energy Resources, it contains nitrogen necessary to a large amount of organic matters and plant growth, phosphorus, potassium
With other middle microelements.The present invention utilizes straw fiber content abundant, is formed and is crosslinked with thermoplastic starch, increases film
Crushing resistance, the mechanical characteristics such as ductility.
Further, degradation plastic is poly butylene succinate, polycaprolactone, poly-β-hydroxybutyric acid in the step S4
Or one of polyhydroxyalkanoate or a variety of.
Further, degradation plastic is poly butylene succinate in the step S4.
Poly butylene succinate (PBS) is easily broken down into carbon dioxide and water in nature, biocompatibility and
Absorbability is preferable, is the Typical Representative of Biodegradable polymer material, and synthetic raw material is abundant, cost is relatively low.
Further, nontoxic plasticizer is one of glycerol, epoxidized soybean oil or tributyl citrate in the step S3
Or it is a variety of.
Plasticizer is a kind of high molecular material auxiliary agent, and this substance is added in plastic processing, its flexibility can be made to increase
By force, it is easily worked, but common plasticiser has certain toxicity, can bring harm to the mankind and animals and plants.Glycerol, epoxy soybean
Oil, these three nontoxic plasticisers of tributyl citrate derive from natural biology or fermentation, safe and non-toxic, environmental-friendly.
Further, starch is food starch in the step S3.
Starch have the advantages that it is from a wealth of sources, cheap, safe and harmless, biodegradable, and be renewable resource, be
To substitute the very good material of petroleum-based plastics.Hydrogen bond structure inside the action breaks down starch of high temperature, shearing force and plasticizer,
So that the arrangement of starch molecule is tended to disordering, reduces its glass transition temperature, make it have thermoplasticity.Common food starch
Including cornstarch, potato starch, starch from sweet potato etc..
Further, organic solvent is one or both of ethyl alcohol or dimethyl sulfoxide in the step S3.
Dimethyl sulfoxide (DMSO) hygroscopicity is good with thermal stability, is a kind of non-proton highly polar atent solvent, can dissolve
In most of organic matters, molecular association ability is stronger, can destroy the ordered structure of starch, is conducive to starch plasticizing, and is formed equal
One amorphous continuous phase, makes the toughness of material be improved.Ethyl alcohol can increase the compatibility of DMSO and starch.
Further, the mill spacing of defibrination is 0.1 ~ 0.5mm in the step S2, and mesh screen is 100 ~ 200 mesh.
Further, in the step S2 when defibrination, solid content is 5 ~ 10%.
Compared with the existing technology, the present invention has the advantage that and effect:
1) packaging film of the invention can be degradable in nature, not can cause environmental pollution；
2) packaging film component of the invention is safe and non-toxic, can be used for food packaging；
3) packaging film of the invention is in excellent in mechanical performance such as tensile strength, elongation at break；
4) raw material sources are abundant, and production cost is low, enriches the resource utilization of stalk；
5) simple production process is controllable, and stability is good, is suitble to large-scale industrial production.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1:
A kind of preparation method of packaging film that can be degradable, includes the following steps:
S1: by corn stover crushed after being dried, broken corn stover 200g is weighed, the NaOH solution of 0.5mol/L is added
600mL, and in 80 DEG C of closed processes 1h, obtain processing feed liquid；
S2: disc mill defibrination process 3 times will be put into, wherein mill spacing is after processing feed liquid described in S1 washs 2 times with clear water
Then 0.1mm crosses 100 mesh mesh screens, takes filtrate that corn stalk fiber slurry is made；
S3: cornstarch and DMSO 1:1 in mass ratio being pre-mixed, then add the glycerol of 10% Maize Starch Content, and 60
DEG C constant temperature under, 1000r/min at the uniform velocity stirs 2h, and until being plasticized, sealing and standing 20h obtains thermoplastic starch；
S4: poly butylene succinate 100g is weighed in 120 DEG C of meltings completely, by the 10g of corn stalk fiber slurry described in S2
It is added in the poly butylene succinate melted in advance simultaneously with thermoplastic starch 500g described in S3, the temperature of melting is 120
DEG C, 150 DEG C are placed in, 30 min are stirred with the speed of 40r/min, the material after plasticating is then taken out, is put into mold, be pressed into
Film.
Embodiment 2:
A kind of preparation method of packaging film that can be degradable, includes the following steps:
S1: by rice straw crushed after being dried, weighing broken rice straw 200g, add the NaOH solution 800mL of 1mol/L,
And in 90 DEG C of closed processes 2h, processing feed liquid is obtained；
S2: after processing feed liquid clear water described in S1 is washed 3 times, defibrination process 4 times, wherein mill spacing is 0.3mm, then mistake
150 mesh mesh screens take filtrate that rice straw fibre stuff is made；
S3: potato starch and ethyl alcohol 1:1 in mass ratio are pre-mixed, then add the epoxy soybean of 15% content of starch
Oil, under 80 DEG C of constant temperature, 2000r/min at the uniform velocity stirs 2h, and until being plasticized, sealing and standing for 24 hours, obtains thermoplastic starch；
S4: polycaprolactone 100g is weighed in 80 DEG C of meltings completely, by heat described in rice straw fibre stuff described in S2 60 and S3
Plastic starch 600g is added in the polycaprolactone melted in advance simultaneously, is placed in 180 DEG C of speed with 50r/min and is stirred 40
Min then takes out the material after plasticating, is put into mold, compacting film forming.
Embodiment 3:
A kind of preparation method of packaging film that can be degradable, includes the following steps:
S1: by broomcorn straw crushed after being dried, broken broomcorn straw 200g is weighed, the NaOH solution of 2mol/L is added
1000mL, and in 100 DEG C of closed processes 1h, obtain processing feed liquid；
S2: after processing feed liquid clear water described in S1 is washed 3 times, defibrination process 5 times, wherein mill spacing is 0.5mm, then mistake
200 mesh mesh screens take filtrate that broomcorn straw fibre stuff is made；
S3: by starch and DMSO, ethyl alcohol 1:1:1 in mass ratio is pre-mixed, then adds the citric acid three of 20% content of starch
Butyl ester, under 90 DEG C of constant temperature, 3000r/min at the uniform velocity stirs 3h, and until being plasticized, sealing and standing for 24 hours, obtains thermoplastic starch
Powder；
S4: poly butylene succinate 100g is weighed in 120 DEG C of meltings completely, by the 150g of plant straw fibers slurry described in S2
It is added in the poly butylene succinate melted in advance simultaneously with thermoplastic starch 1kg described in S3,200 DEG C is placed in, with 60r/
The speed of min stirs 50 min, then takes out the material after plasticating, is put into mold, compacting film forming.
Experimental example 1
To packaging film prepared by the embodiment of the present invention 1,2,3, the sample that specification is 40mm*10mm*0.2mm is made, passes through plastics
Erichsen test method tests mechanical property, and testing standard stretches speed using electronic tensile machine referring to GB/T1040-1992
Degree is 3.33mm per second, tests the elongation at break of degradable material, tearing strength completes the detection of tensile strength；
Table 1
As can be seen from the above table, packaging film prepared by the present invention has excellent tensile strength and elongation at break.
Experimental example 2
To packaging film prepared by the embodiment of the present invention 1,2,3, biodegradability is tested, biology drop is completed using soil buries method herein
The detection for solving performance, is first made the identical thin slice of size for sample with equal proportion, then places into the soil, and takes after 6,12 months
Sample weighs up its weight out, and the biological degradation rate (Degradability) of sample can be calculated by weight-loss ratio, and formula is such as
Under:
Degradation rate=(W0-Wt)/W0×100%。
The embodiment of the present invention 1,2,3 prepare packaging film degradable material place into the soil after 6 months, biological degradation rate can reach
73%, 80%, 77%, effectively reach degradation purpose.
The embodiment of the present invention 1,2,3 prepare packaging film degradable material place into the soil after 12 months, biological degradation rate reaches
To 100%, degradation purpose is effectively reached.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. the preparation method for the packaging film that one kind can be degradable, which is characterized in that described method includes following steps:
S1: by straw crushed after being dried, the NaOH water of 0.5 ~ 2mol/L is added by 3 ~ 5 times of quality of straw after crushing
Solution, and in 80 ~ 100 DEG C of 1 ~ 3h of closed processes, obtain processing feed liquid；
S2: after processing feed liquid described in step S1 is washed with water 2 ~ 3 times, defibrination process 3 ~ 5 times, mesh screen is then crossed, filtrate system is taken
Obtain plant straw fibers slurry；
S3: starch and organic solvent 1:1 ~ 3 in mass ratio are pre-mixed, then add the nontoxic increasing of 10 ~ 20% content of starch
Agent is moulded, under 60 ~ 90 DEG C of constant temperature, 1000 ~ 4000r/min at the uniform velocity stirs 2 ~ 3h, until being plasticized, sealing and standing 20 ~
For 24 hours, thermoplastic starch is obtained；
S4: it plasticates: by thermoplastic starch described in plant straw fibers slurry described in step S2 and step S3 while being added to pre-
In the degradation plastic first melted, 30 ~ 50 min are stirred with the speed of 40 ~ 60r/min at a temperature of 150 ~ 200 DEG C, are then taken out
Material after plasticating, calendering or film extrusion, wherein plant straw fibers slurry account for thermoplastic starch mass percent be 5 ~
15%, the weight of thermoplastic starch is 5 ~ 10 times of degradation plastic.
2. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that the straw is
One of corn stover, rice straw or broomcorn straw are a variety of.
3. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that can in the step S4
Degradative plastics is one of poly butylene succinate, polycaprolactone, poly-β-hydroxybutyric acid or polyhydroxyalkanoate or more
Kind.
4. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that nothing in the step S3
Malicious plasticizer is one of glycerol, epoxidized soybean oil or tributyl citrate or a variety of.
5. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that form sediment in the step S3
Powder is food starch.
6. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that have in the step S3
Solvent is one or both of ethyl alcohol or dimethyl sulfoxide.
7. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that ground in the step S2
The mill spacing of slurry is 0.1 ~ 0.5mm, and mesh screen is 100 ~ 200 mesh.
8. the preparation method of packaging film that according to claim 1 can be degradable, which is characterized in that ground in the step S2
When slurry, solid content is 5 ~ 10%.
9. a kind of packaging film that claim 1 ~ 8 any one the method is prepared.
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| CN201811603854.3A CN109824924A (en) | 2018-12-26 | 2018-12-26 | A kind of packaging film and preparation method thereof that can be degradable |
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| CN201811603854.3A CN109824924A (en) | 2018-12-26 | 2018-12-26 | A kind of packaging film and preparation method thereof that can be degradable |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343397A (en) * | 2019-07-02 | 2019-10-18 | 汕头市雷氏塑化科技有限公司 | A kind of bamboo powder full-biodegradable material and preparation method thereof |
| CN110862584A (en) * | 2019-10-30 | 2020-03-06 | 河南晖睿智能科技有限公司 | Preparation method of environment-friendly degradable novel material |
| CN111423625A (en) * | 2020-05-26 | 2020-07-17 | 安徽颍美科技股份有限公司 | Preparation method of environment-friendly packaging material based on modified corn starch |
| CN112142987A (en) * | 2020-10-15 | 2020-12-29 | 中国科学院长春应用化学研究所 | Modified starch, preparation method thereof, starch film and preparation method thereof |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811603854.3A patent/CN109824924A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343397A (en) * | 2019-07-02 | 2019-10-18 | 汕头市雷氏塑化科技有限公司 | A kind of bamboo powder full-biodegradable material and preparation method thereof |
| CN110862584A (en) * | 2019-10-30 | 2020-03-06 | 河南晖睿智能科技有限公司 | Preparation method of environment-friendly degradable novel material |
| CN111423625A (en) * | 2020-05-26 | 2020-07-17 | 安徽颍美科技股份有限公司 | Preparation method of environment-friendly packaging material based on modified corn starch |
| CN112142987A (en) * | 2020-10-15 | 2020-12-29 | 中国科学院长春应用化学研究所 | Modified starch, preparation method thereof, starch film and preparation method thereof |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
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Application publication date: 20190531 |