CN109575540A - A kind of vinasse polylactic acid biodegradable composites, preparation method and application - Google Patents
A kind of vinasse polylactic acid biodegradable composites, preparation method and application Download PDFInfo
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- CN109575540A CN109575540A CN201811455579.5A CN201811455579A CN109575540A CN 109575540 A CN109575540 A CN 109575540A CN 201811455579 A CN201811455579 A CN 201811455579A CN 109575540 A CN109575540 A CN 109575540A
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- Prior art keywords
- vinasse
- polylactic acid
- biodegradable composites
- acid 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
- 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
Abstract
The invention discloses a kind of vinasse polylactic acid biodegradable composites, preparation method and application, are related to degradable material technical field.Described vinasse polylactic acid biodegradable composites and preparation method thereof, by weight, which includes following components: 5~40 parts of spirit stillage, 50~90 parts of polylactic acid, 5~10 parts of environment-friendly plasticizer, 0.1~0.5 part of antioxidant.The present invention also proposes the application of above-mentioned and vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto.The present invention prepares degradable composite material using vinasse as filler, it can replace the crops, the forest reserves such as starch, bamboo fibre, improve the utilization rate of white wine by-product, preparation method is simple, vinasse raw material only need to be by simple pretreating process such as dry, crushing, vinasse polylactic acid biodegradable composites obtained can be used for Wine packaging (packaging bag and Neto), form the demonstration effect of liquor industry resource circulation utilization.
Description
Technical field
The present invention relates to degradable high polymer material forming processing technology field more particularly to a kind of vinasse polylactic acid are high-fall
Solve composite material, preparation method and application.
Background technique
Current degradable, green, environment-friendly package material is more and more sustainable by the attention of the majority of consumers, and future
Contradictory the only way which must be passed of resource and environment that sexual development, solution increasingly aggravate.More and more materials, which are exploited out, can be used for making
Standby biodegradation material, such as:
Patent of invention CN103254591B discloses vinasse/PBS composite material and its preparation, however basis material used
PBS, yield is lower, and price is higher, is not suitable for large-scale promotion application, and the composite material is adsorbed for thorium waste liquid, no body of laws
The value that existing vinasse are recycled in liquor industry.
Patent of invention CN106317809B discloses a kind of biology base degradable anti-flaming polylactic acid engineering material and its preparation
Method is formed by polylactic acid, surface treated spirit stillage and polymer electrolyte phosphonium flame retardant melting mixing, and vinasse need
By in deionized water, stirring is filtered, washing, drying, the multi step strategies such as sieving, complex process；And the material is as fire-retardant
Engineering material uses, and needs higher processing temperature (170~190 DEG C), and energy consumption is high.
Patent of invention CN201710022473.5 discloses the biodegradable flowerpot material utilized of one kind and its preparation side
Method, by polylactic acid, vinasse, precipitated calcium carbonate, tributyl citrate, silane coupling agent is made.Due to having used inorganic filler living
Property precipitated calcium carbonate, need additionally use silane coupling agent reinforcing filler and polylactic resin matrix interface binding power, increase
Cost；The blending method disposably to be fed intake using all raw materials and auxiliary agent is unfavorable for auxiliary agent and played a role；And to polylactic acid into
It has gone specially treated, has been able to maintain its performance in use and non-degradable, causes biodegradable availability low.
For another example, patent of invention CN201810444029.7 discloses a kind of biodegradable plastic packaging bag material utilized
And preparation method thereof, it is made of polyvinyl alcohol, vinasse, monohydrate potassium, glycerol, distilled water, the preparation to be formed a film using liquid phase
Method, production efficiency are lower；However, Water-Resistance of PVA is poor, the strength of materials is lower, is generally only used for production film bag and produces
Product.
Summary of the invention
The technical problem to be solved by the present invention is to how make full use of white wine by-product to realize, Industrial Resources are recycled.
To solve the above-mentioned problems, the present invention proposes following technical scheme:
In a first aspect, the present invention proposes a kind of vinasse polylactic acid biodegradable composites, by weight, including with the following group
Point: 5~40 parts of spirit stillage, 50~90 parts of polylactic acid, 5~10 parts of environment-friendly plasticizer, 0.1~0.5 part of antioxidant.
Further technical solution is for it, and the spirit stillage is Poly-grain type spirit stillage or single grain type spirit stillage.
Further technical solution is for it, the environment-friendly plasticizer, be glycerol, triethyl citrate, tributyl citrate,
At least one of acetyl trihexyl citrate.
Further technical solution is for it, the antioxidant, is antioxidant 1010 or antioxidant 2246.
Second aspect, the present invention propose that vinasse polylactic acid biodegradable composites as described in relation to the first aspect make Wine packaging
The application of bag and/or bottle Neto.
The third aspect, the present invention propose a kind of preparation of vinasse polylactic acid biodegradable composites as described in relation to the first aspect
Method, comprising the following steps:
Vinasse after drying are uniformly mixed with environment-friendly plasticizer in proportion, obtain premix by S1；
In proportion the premix is added in antioxidant and polylactic acid by S2, and dispersion mixes, and obtains blend composition；
The blend composition is carried out co-extrusion pelletizing by S3 at 140-180 DEG C, and through cooling and dicing, as the vinasse are poly-
Lactic acid biodegradable composites.
Further technical solution is for it, further includes before the step S1, mistake after vinasse are dried at 50-70 DEG C
60-100 mesh.
Further technical solution is for it, further includes before the step S2, by polylactic acid at 50-70 DEG C at drying
Reason.
Compared with prior art, the attainable technical effect of present invention institute includes:
First, the vinasse that the present invention utilizes are the by-products of liquor industry, prepare degradable composite material as filler, can
Instead of the crops such as starch, bamboo fibre, the forest reserves, the utilization rate of white wine by-product is improved, is reduced to crops, the forest reserves
Consumption, realize resource reutilization；Use polylactic acid as the matrix of biodegradation material, without selecting PBS or other biological
Degradative resin is because polylactic acid has technical maturity, the advantages such as yield is big, and price is low；It can be further using environment-friendly plasticizer
The degradability of composite material entirety is improved, the requirement to degradable material in the world is met；Add antioxidant, Ke Yishi
When the degradation rate for reducing vinasse lactic acid composite material, the service life of Wines packing accessory is appropriately extended, more fitting wine packet
The application scenarios of dress.
Second, the preparation method of vinasse polylactic acid biodegradable composites proposed by the present invention is simple, and vinasse raw material only needs
By the simple pretreating process such as drying, crushing, without carrying out the complex process techniques such as washing suction filtration；When mixing, first by vinasse
Powder is sufficiently mixed with plasticizer, then with polylactic acid blend, can improve the dispersibility of vinasse filler, improve vinasse and polylactic acid mixing
With the compatibility during melt-processed, while processing temperature is effectively reduced, reduces energy consumption.
Third, vinasse polylactic acid biodegradable composites processing performance and mechanical performance produced by the present invention are superior, can answer
For Wine packaging (packaging bag and Neto), industrialization is realized, form the demonstration effect of liquor industry resource circulation utilization.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.Obviously, it will be described below embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction
Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded
Body, step, operation, the presence or addition of element, component and/or its set.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementation
Example purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present invention
As use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrap
Include plural form.
Embodiment 1
The present embodiment proposes a kind of vinasse polylactic acid biodegradable composites, including following component: dry vinasse 5g, lemon
Lemon acid tributyl 5g, polylactic acid 90g, antioxidant 1010 0.1g.
The present embodiment also proposes a kind of preparation method of vinasse polylactic acid biodegradable composites, comprising: by vinasse and gathers
Lactic acid is dried respectively at 50 DEG C, and vinasse cross 60 meshes；The vinasse of sieving are uniformly mixed with tributyl citrate
To premix, high-speed mixer is added in premix, polylactic acid, antioxidant 1010 is added, is mixed with the revolving speed of 4000rpm
10min makes it be uniformly dispersed, and obtains blend composition；Blend composition is added twin-screw extrude and carries out melt blending (temperature is
180 DEG C, revolving speed 60rpm), through supercooling, pelletizing is to get vinasse polylactic acid biodegradable composites.
The present embodiment also proposes a kind of vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto
Using.
Vinasse polylactic acid biodegradable composites obtained are passed through into injection molding, bottle Neto can be made.
Vinasse polylactic acid biodegradable composites obtained are passed through into blowfilm shaping, Wine packaging bag can be made.
It should be noted that in the preparation method of the proposition of the present embodiment, in order to enable each component is uniformly mixed, mixing side
Just, therefore mixed using high-speed mixer, mix revolving speed and incorporation time can sets itself, reach uniformly mixed mesh
, in other embodiments, technical staff can also be used the mode of other machines or hand operated mixing to carry out material mixing.
It should be noted that carrying out co-extrusion pelletizing using double screw extruder in the preparation method of the proposition of the present embodiment
Operation, in other embodiments, technical staff can voluntarily select extruder according to the actual situation, and the present invention does not do specific limit to this
It is fixed.
It should be noted that the present invention passes through blowfilm shaping and injection molding using vinasse polylactic acid biodegradable composites
Technique made from Wine packaging bag and/or bottle Neto, be prior art means, those skilled in the art can also pass through other works
Skill does not do specific limit to this using vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto, the present invention
It is fixed.
Vinasse are remaining residues after the wine brewing such as rice, wheat, jowar, and main component is crude fibre, Crude starch, crude protein, nothing
The biodegradable polymers such as nitrogen extract.
It is an object of the invention to be blended with degradable polyesters such as polylactic acid multiple using vinasse as the filler of cheap environmental protection
It closes, prepares biodegradable composites, be reused for Wine packaging (packaging bag and Neto), form liquor industry resource circulation utilization
Demonstration effect.
Use liquor-making byproduct vinasse as filler, instead of the starch that generallys use (usually by corn, potato, cassava
Etc. edibilities crop), it is possible to reduce the consumption to food crop；Bamboo fibre, the plant fibers such as wood-fibred are substituted, it can be with
The consumption to the forest reserves is reduced, the multisteps preprocessing process such as washing suction filtration is needed not move through, is resource-conserving, environmentally friendly
Degradable packing material.
Use polylactic acid as the matrix of biodegradation material, without selecting PBS or other biological degradative resin, be because
Polylactic acid has technical maturity, and the advantages such as yield is big, and price is low come biodegradable composites large-scale production and application
It says, practicability and economy are higher.
Use glycerol, triethyl citrate, tributyl citrate, acetyl trihexyl citrate as environment-friendly plasticizer, has
There is the advantages of non-toxic degradable；Composite material entirety Wholly-degradable is further increased, is met in the world to degradable material
The requirement of material enhances compatibility without using inorganic filler and silane coupling agent.
In composite material preparation process, vinasse raw material only need to be by simple pretreating process such as dry, sievings, without carrying out
The complex process techniques such as washing suction filtration；When mixing, first vinasse and plasticizer are sufficiently mixed, then with polylactic acid blend, can improve
The dispersibility of vinasse filler improves the compatibility during vinasse and polylactic acid mixing and melt-processed, while being effectively reduced and adding
Work temperature reduces energy consumption.
Antioxidant is added, the degradation rate of vinasse lactic acid composite material can be suitably reduced, drinks packet is appropriately extended
The service life of assembly parts is more bonded the application scenarios of Wine packaging.
Embodiment 2
The present embodiment proposes a kind of vinasse polylactic acid biodegradable composites, including following component: dry vinasse 10g,
Triethyl citrate 7g, polylactic acid 80g, antioxidant 1010 0.2g.
The present embodiment also proposes a kind of preparation method of vinasse polylactic acid biodegradable composites, comprising: by vinasse and gathers
Lactic acid is dried respectively at 60 DEG C, and vinasse cross 70 meshes；The vinasse of sieving are uniformly mixed with triethyl citrate
To premix, mixing machine is added in premix, polylactic acid, antioxidant 1010 is added, with the revolving speed mixing 10min of 4000rpm,
So that it is uniformly dispersed, obtains blend composition；Progress melt blending in extruder is added in blend composition, and (temperature is 140 DEG C, and revolving speed is
120rpm), through supercooling, pelletizing is to get vinasse polylactic acid biodegradable composites.
The present embodiment also proposes a kind of vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto
Using.
Vinasse polylactic acid biodegradable composites obtained are passed through into injection molding, bottle Neto can be made.
Vinasse polylactic acid biodegradable composites obtained are passed through into blowfilm shaping, Wine packaging bag can be made.
Embodiment 3
The present embodiment proposes a kind of vinasse polylactic acid biodegradable composites, including following component: dry vinasse 20g,
Acetyl trihexyl citrate 8.5g, polylactic acid 70g, 2246 0.3g of antioxidant.
The present embodiment also proposes a kind of preparation method of vinasse polylactic acid biodegradable composites, comprising: by vinasse and gathers
Lactic acid is dried respectively at 70 DEG C, and vinasse sieve with 100 mesh sieve；The vinasse of sieving are mixed with acetyl trihexyl citrate
It is even to obtain premix, mixing machine is added in premix, polylactic acid, antioxidant 2246 is added, is mixed with the revolving speed of 4000rpm
10min makes it be uniformly dispersed, and obtains blend composition；Progress melt blending in extruder is added in blend composition, and (temperature is 160 DEG C, is turned
Speed is 100rpm), through supercooling, pelletizing is to get vinasse polylactic acid biodegradable composites.
The present embodiment also proposes a kind of vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto
Using.
Vinasse polylactic acid biodegradable composites obtained are passed through into injection molding, bottle Neto can be made.
Vinasse polylactic acid biodegradable composites obtained are passed through into blowfilm shaping, Wine packaging bag can be made.
Embodiment 4
The present embodiment proposes a kind of vinasse polylactic acid biodegradable composites, including following component: dry vinasse 40g,
Glycerol 10g, polylactic acid 50g, 2246 0.5g of antioxidant.
The present embodiment also proposes a kind of preparation method of vinasse polylactic acid biodegradable composites, comprising: by vinasse and gathers
Lactic acid is dried respectively at 60 DEG C, and vinasse cross 90 meshes；The vinasse of sieving are uniformly mixed to obtain premix with glycerol,
High-speed mixer is added in premix, polylactic acid, antioxidant 2246, which is added, with the revolving speed mixing 10min of 4000rpm makes it
It is uniformly dispersed, obtains blend composition；Blend composition is added twin-screw extrude progress melt blending, and (temperature is 150 DEG C, and revolving speed is
90rpm), through supercooling, pelletizing is to get vinasse polylactic acid biodegradable composites.
The present embodiment also proposes a kind of vinasse polylactic acid biodegradable composites production Wine packaging bag and/or bottle Neto
Using.
Vinasse polylactic acid biodegradable composites obtained are passed through into injection molding, bottle Neto can be made.
Vinasse polylactic acid biodegradable composites obtained are passed through into blowfilm shaping, Wine packaging bag can be made.
Comparative example 5
Vinasse and polylactic acid are dried respectively at 55 DEG C, and vinasse cross 80 meshes；By the vinasse 20g and lemon of sieving
High-speed mixer is added in lemon acid tributyl 8.5g, polylactic acid 70g, antioxidant 1010 0.3g, is mixed with the revolving speed of 4000rpm
10min makes it be uniformly dispersed, and obtains blend composition；Blend composition is added twin-screw extrude and carries out melt blending (temperature is
180 DEG C, revolving speed 60rpm), through supercooling, pelletizing is to get composite material.
Above-mentioned composite material is passed through into injection molding, bottle Neto is made.
Comparative example 6
Vinasse are placed in a certain amount of deionized water, wherein the ratio of vinasse and water is 1:100, stirs 30min, is taken out
Filter, drying, crosses 80 meshes at washing, is made through the pretreated vinasse of multistep, weighs the pretreated vinasse 20g of multistep and lemon
Sour tributyl 8.5g is uniformly mixed and obtains premix, and high-speed mixer is added in premix, pretreated polylactic acid is added
70g, antioxidant 1010 0.3g obtain blend composition with the revolving speed mixing 10min of 4000rpm；Twin-screw is added in blend composition
Melt blending (extruder temperature is 180 DEG C, revolving speed 60rpm) is carried out in extruder, through supercooling, pelletizing is to get composite material；
Using injection molding, bottle Neto is made.
Performance test
The composite material being prepared by embodiment 1, comparative example 5 and comparative example 6 is chosen, by measuring relevant parameter,
Obtain the following table 1:
Table 1 is to composite material experimental result made from embodiment 1, comparative example 5 and comparative example 6
It can be seen from the experiment that there is excellent mechanical property using the modified polylactic acid biodegradable composites of vinasse, especially
It has been to maintain the higher-strength performance of polylactic acid.Wherein, by vinasse and environment-friendly plasticizer premix after again with polylactic acid blend papermaking
Manufactured composite material (embodiment 1, comparative example 6), processing performance and mechanical performance are better than whole components blending granulations and are made
Composite material (comparative example 5)；Though composite material made from comparative example 6 equally has good processing performance and mechanical performance,
It is inefficiency in actual production, at high cost however, carry out the washing complicated technologies such as suction filtration during the preparation process；Compare and
Speech, embodiment 1 only needs drying to the preprocessing process of vinasse, without filter the process of washing, simply, conveniently, cost
Low, composite processing performance and mechanical performance obtained are superior, are more advantageous to realization industrialization.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodiment
Part, reference can be made to the related descriptions of other embodiments.
The above is a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, any ripe
It knows those skilled in the art in the technical scope disclosed by the present invention, various equivalent modifications can be readily occurred in or replaces
It changes, these modifications or substitutions should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with right
It is required that protection scope subject to.
Claims (8)
1. a kind of vinasse polylactic acid biodegradable composites, which is characterized in that by weight, including following components: dry
5~40 parts of vinasse, 50~90 parts of polylactic acid, 5~10 parts of environment-friendly plasticizer, 0.1~0.5 part of antioxidant.
2. vinasse polylactic acid biodegradable composites as described in claim 1, which is characterized in that the vinasse are that Poly-grain type is white
Wine vinasse and/or single grain type spirit stillage.
3. vinasse polylactic acid biodegradable composites as described in claim 1, which is characterized in that the environment-friendly plasticizer is
At least one of glycerol, triethyl citrate, tributyl citrate, acetyl trihexyl citrate.
4. vinasse polylactic acid biodegradable composites as described in claim 1, which is characterized in that the antioxidant is anti-
Oxidant 1010 or antioxidant 2246.
5. vinasse polylactic acid biodegradable composites production Wine packaging bag according to any one of claims 1-4 and/or bottle
The application of Neto.
6. a kind of preparation method of vinasse polylactic acid biodegradable composites according to any one of claims 1-4, feature
It is, comprising:
Vinasse after drying are uniformly mixed with environment-friendly plasticizer in proportion, obtain premix by S1；
In proportion the premix is added in antioxidant and polylactic acid by S2, and dispersion mixes, and obtains blend composition；
The blend composition is carried out co-extrusion pelletizing by S3 at 140-180 DEG C, through cooling and dicing, the as described vinasse polylactic acid
Biodegradable composites.
7. the preparation method of vinasse polylactic acid biodegradable composites as claimed in claim 6, which is characterized in that the step
It further include that vinasse are crossed into 60-100 mesh at 50-70 DEG C after drying before S1.
8. the preparation method of vinasse polylactic acid biodegradable composites as claimed in claim 6, which is characterized in that the step
It further include being dried polylactic acid at 50-70 DEG C before S2.
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Cited By (5)
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| CN111320815A (en) * | 2020-03-20 | 2020-06-23 | 贵州华清科维环境能源有限责任公司 | Method for extracting vinasse fiber component from vinasse for wood-plastic production |
| CN114196216A (en) * | 2021-12-27 | 2022-03-18 | 杭州靡特洛新材料科技有限公司 | Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof |
| WO2022071800A1 (en) | 2020-09-30 | 2022-04-07 | Coda Intellectual Property B.V. | Polymer composite comprising spent grains and/or grape pomace |
| CN114479503A (en) * | 2021-12-29 | 2022-05-13 | 青海互助青稞酒股份有限公司 | Highland barley vinasse biodegradable material and preparation method and application thereof |
| NL2026594B1 (en) * | 2020-09-30 | 2022-06-01 | Coda Intellectual Property B V | Polymer composite comprising spent grains |
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| CN114479503A (en) * | 2021-12-29 | 2022-05-13 | 青海互助青稞酒股份有限公司 | Highland barley vinasse biodegradable material and preparation method and application thereof |
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