CN108948691A - A kind of lignin modification starch base PHA biodegrade membrane material and preparation method thereof - Google Patents
A kind of lignin modification starch base PHA biodegrade membrane material and preparation method thereof Download PDFInfo
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- CN108948691A CN108948691A CN201710353050.1A CN201710353050A CN108948691A CN 108948691 A CN108948691 A CN 108948691A CN 201710353050 A CN201710353050 A CN 201710353050A CN 108948691 A CN108948691 A CN 108948691A
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- pha
- starch base
- biodegrade
- lignin
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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
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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
Abstract
The invention discloses a kind of lignin modification starch base PHA biodegrade membrane material and preparation method thereof, the preparation method include: (1) by starch base polyhydroxyalkanoate (PHA) particle, lignin respectively into vacuum drying；(2) starch base polyhydroxyalkanoate (PHA) particle, lignin and chain extender, antioxidant, plasticizer, lubricant, heat stabilizer after drying is added in high mixer, are uniformly mixed；(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization；(4) by the composite plastic grain carry out at a certain temperature blown film to get.Using lignin modification starch base PHA biodegrade membrane material made from the method for the present invention, while meeting degradable requirement after composite modified, the mechanical property of starch base PHA resin is enhanced, and effectively reduces production cost, is more advantageous to marketing.
Description
Technical field
The present invention relates to degradative plastics technical field more particularly to a kind of lignin modification starch base PHA Biodegradable films
Material and preparation method thereof.
Background technique
Currently, the consumption figure of plastic products is constantly increasing, and synthetic plastic is producing with the continuous development of national economy
It is played an increasingly important role in life.But can not degrade after being discarded due to most plastic products, it deposits for a long time
, constantly accumulation causes serious white pollution, and continuous with pollution is aggravated and the continuous enhancing of people's environmental consciousness,
Seeking a kind of plastic products for being not only able to satisfy people's use demand but also being able to satisfy ecological requirements seems more more and more urgent and causes
The broad interest of researcher, wherein degradable resin has become the heat of research due to its degradation characteristic and economic performance
Point,
Polyhydroxyalkanoate (polyhydroxyalkanoates, PHA) develops rapidly, is for nearly more than 20 years
A kind of intracellular polyester of many Microbe synthesis is a kind of natural polymeric biomaterial.Since PHA has well simultaneously
Bio-compatible performance, the hot-working character of biodegradability and plastics, so it at the same time as bio-medical material and
Biodegradable packaging material, therefore it has become the research hotspot that technical field of biological material is the most active in recent years.PHA also has
There are optically nonlinearity, piezoelectricity, gas phase every many high added value performances of property.Natural or synthesis biodegradable height
Molecular material often has very high water vapo(u)r transmission, this is unfavorable in food fresh keeping.And PHA then has good gas
Barrier property makes it possible to apply in the fresh goods fresh-keeping packaging of long period.Because penetrating for steam is weight in fresh-keeping packaging
Want index, the performance of PHA in this regard is can to compare completely with products such as present PET, PP etc..Separately-aspect, PHA
Also there is preferable hydrolytic stability, the cup made of PHA is always washed into 20 circulations, its shape with 75 DEG C of automatic dish-washing machine
Shape and molecular weight show that PHA can perform well in utensil production all there is no variation.Furthermore with other polyolefins,
Polyaromatic quasi polymer ratio, PHA also have good ultraviolet stability.PHA is alternatively arranged as biodegradable environmentally friendly solvent
Source, as ethyl hydroxy-acid EHB (ethyl3-hydroxy-butyrate) be it is water-soluble, poly- have low volatility, can be with
For detergent, glue) stick, dyestuff, ink solvent.Just because of PHA summarizes these excellent performances, allow to wrapping
Package material, jointing material, sprayed on material and dress material, utensil class material, electronic product, durable consumer goods, agricultural products, automation
It is applied in the fields such as product, chemical mediator and solvent.But PHA is due to its fancy price cost (PHA pure resin price
At four times or more of general plastics), it significantly limits this biodegradable plastic and promotes in the market, starch is a kind of tool
There are the bio-based materials in extensive source, it may have excellent biodegradation character, while starch has relatively very cheap valence
Lattice are had been widely used at present in biodegradable field, and major way is the mode that processing is blended with biodegradable plastic,
But since its mechanical property is general, to also limit its application as material
Lignin be in a kind of unformed, molecular structure being widely present in plant containing oxo phenylpropanol or its
The armaticity high polymer of derivant structure unit.Since there is aromatic radicals for the molecular structure of lignin.Phenolic hydroxyl group, alcoholic extract hydroxyl group,
Carbon-based conjugated double bond isoreactivity group, thus can by oxidation, reduction, hydrolysis, alcoholysis, acidolysis methoxyl group, carboxyl, phthalein,
A variety of reactive modes such as sulfonation, alkylation, halogenation, polycondensation or graft copolymerization are modified.Lignin has preferable mechanics
Performance and wooden appearance attribute, while from biomass resource, simultaneously under composting conditions with degradability quickly
Can, it is a kind of following more environmentally protective material.
Summary of the invention
The object of the present invention is to provide a kind of lignin modification starch base PHA biodegrade membrane materials and preparation method thereof.
The present invention introduces biological material lignin on the basis of biodegradation material starch base PHA, after composite modified
While meeting degradable requirement, the mechanical property of starch base PHA material is enhanced, and effectively reduces this kind of plastics
Cost is obtained, is allowed to be more advantageous to marketing.
To achieve the above object, the invention adopts the following technical scheme:
The first aspect of the invention is to provide a kind of preparation side of lignin modification starch base PHA biodegrade membrane material
Method specifically comprises the following steps:
(1) by starch base polyhydroxyalkanoate (PHA) particle, lignin respectively into vacuum drying；
(2) starch base polyhydroxyalkanoate (PHA) particle, lignin and chain extension after drying are added in high mixer
Agent, antioxidant, plasticizer, lubricant, heat stabilizer are uniformly mixed, and mixed material is made；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, it is compound that lignin-starch base PHA is made
Plastic pellet；
(4) the composite plastic grain is subjected to blown film at a certain temperature, prepares the PHA biodegrade of lignin modification starch base
Membrane material.
Further, in the preparation method of the lignin modification starch base PHA biodegrade membrane material, by weight
Number meter, each raw material dosage proportion are as follows:
It is further preferred that being pressed in the preparation method of the lignin modification starch base PHA biodegrade membrane material
Parts by weight meter, each raw material dosage proportion are as follows:
Further more preferably, in the preparation method of the lignin modification starch base PHA biodegrade membrane material
In, according to parts by weight, each raw material dosage proportion is as follows:
Further, in the preparation method of the lignin modification starch base PHA biodegrade membrane material, each raw material
Weight fraction be 100% to calculate according to raw material effective content, actual amount need to convert according to the actually active content of raw material.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (1)
In, content of starch is 20-35% in starch base polyhydroxyalkanoate (PHA) particle.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (1)
In, lignin is original powder, and particle size range is 100~800 mesh；Preferably 150-600 mesh；Preferably 200~500 mesh；More preferably
For 250~350 mesh.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (1)
In, drying temperature is 25~40 degrees Celsius, and drying time is 1.5h~3h, and vacuum degree is 0~5000Pa (absolute pressure)；It is preferred that
Ground, drying temperature are 28~35 degrees Celsius, and drying time is 2h~3h, and vacuum degree is 400~3000Pa (absolute pressure)；More
Preferably, drying temperature is 30~32 degrees Celsius, drying time 2.5h, and vacuum degree is 1000~1500Pa (absolute pressure).
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (2)
In, heat stabilizer is one of maleic anhydride, epoxidized soybean oil；Lubricant be calcium stearate, in zinc stearate or
Any one of oleamide series lubricant agent or two kinds or more mixture；Plasticizer be tributyl citrate, triethyl citrate,
The compound of any one of acetyl tri-n-butyl citrate, triacetyl glycerine, dibutyl sebacate or two kinds or more.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (2)
In, antioxidant is butylated hydroxy anisole, dibutyl hydroxy toluene, butyl to biphenol, phosphorous acid benzene diisodecyl ester, season penta
Tetrol bis-phosphite, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionate, (2, the 4- bis- tertiary fourths of phosphorous acid three
Base phenyl) ester, one of ten caprylate of 3,5- di-tert-butyl-hydroxy phenyl propionic acid or two or more compounds；Expand
Chain agent be hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, ethylene glycol, 1,4- butanediol, 1,6- oneself two
One of alcohol, diethylene glycol or two or more compounds.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (3)
In, extrusion temperature is 150~200 DEG C；Preferably, extrusion temperature is 160~190 DEG C；More preferably, extrusion temperature 165
~170 DEG C.
Further, the preparation method of the lignin modification starch base PHA biodegrade membrane material the step of (4)
In, blown film temperature is 140~180 DEG C；Preferably, blown film temperature is 140~175 DEG C；More preferably, blown film temperature is 150
~160 DEG C.
The second aspect of the invention is to provide a kind of lignin modification starch base PHA biology using above method preparation
Degradation membrane material.
The third aspect of the invention is to provide a kind of lignin modification starch base PHA biodegrade membrane material in life
It is applied in the fields such as object degradation shopping bag, refuse bag, mulch, green house of vegetables film.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
It is biological to starch base PHA come the lignin prepared that present invention employs the biomass being widely present from nature
Degradative resin is modified modification to be prepared for lignin-starch base PHA composite biological degradation plastic, can be widely used for infusing
Modeling, plastic uptake, sheet material, elastomer, the membrane materials such as hot melt adhesive and shopping bag, refuse bag, mulch, awning film, relative to traditional
Starch base PHA material, the present invention can effectively promote the mechanical property of membrane material, and reduce starch base PHA biodegrade
The cost of finished material makes it easier to marketing.
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
The preparation of 1 lignin modification starch base PHA biodegrade membrane material of embodiment
(1) proportion (mass ratio) of raw material is as follows:
(2) it matches according to above-mentioned raw materials, is prepared using following steps:
(1) a certain amount of starch base PHA, lignin powder (200 mesh) are dried to 2.5h under the conditions of 25 degree, 0~5000Pa；
(2) be added in high mixer dried starch base PHA, lignin powder, 1,6-HD, butyl to biphenol,
Triethyl citrate, epoxidized soybean oil, calcium stearate mix 15 minutes；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, it is compound that lignin-starch base PHA is made
Plastic pellet；
(4) composite plastic is passed through into blown film, can be made into various biodegradable plastic membrane materials.
The preparation of 2 lignin modification starch base PHA biodegrade membrane material of embodiment
(1) proportion (mass ratio) of raw material is as follows:
(2) it matches according to above-mentioned raw materials, is prepared using following steps:
(1) a certain amount of starch base PHA, lignin (200 mesh) are dried to 3h under the conditions of 25 degree, 0~5000Pa；
(2) dried starch base PHA, lignin, acetyl tri-n-butyl citrate, resorcinol are added in high mixer
Dihydroxyethyl ether, butyl mix biphenol, epoxidized soybean oil, calcium stearate 20 minutes；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, it is compound that lignin-starch base PHA is made
Plastic pellet；
(4) composite plastic is passed through into blown film, can be made into various biodegradable plastic membrane materials.
The preparation of 3 lignin modification starch base PHA biodegrade membrane material of embodiment
(1) proportion (mass ratio) of raw material is as follows:
(2) it matches according to above-mentioned raw materials, is prepared using following steps:
(1) a certain amount of starch base PHA, lignin (200 mesh) are dried to 3h under the conditions of 25 degree, 0~5000Pa；
(2) be added in high mixer it is dry after starch base PHA, lignin, maleic anhydride, triacetyl glycerine,
Butyl mixes biphenol, 1,4- butanediol, zinc stearate 25 minutes；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, it is compound that lignin-starch base PHA is made
Plastic pellet；
(4) composite plastic is passed through into blown film, can be made into various biodegradable plastic membrane materials.
The preparation of 4 lignin modification starch base PHA biodegrade membrane material of embodiment
(1) proportion (mass ratio) of raw material is as follows:
(2) it matches according to above-mentioned raw materials, is prepared using following steps:
(1) a certain amount of starch base PHA, lignin (300 mesh) are dried to 3h under the conditions of 25 degree, 0~5000Pa；
(2) starch base PHA, lignin, triacetyl glycerine, bisphenol-A, phosphorous acid benzene after drying is added in high mixer
Diisodecyl ester, epoxidized soybean oil, zinc stearate mix 25 minutes；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, it is compound that lignin-starch base PHA is made
Plastic pellet；
(4) composite plastic is passed through into blown film, can be made into various biodegradable plastic membrane materials.
Performance test:
The starch base polyhydroxyalkanoate (PHA) of unmodified Shenzhen Yi Keman Biotechnology Co., Ltd production is made
For comparative example 1, using universal electrical tensile testing machine (SUN500 type is manufactured by Italian GALDABINI company) respectively to upper
It states embodiment 1-4, the tensile strength of 1 material of comparative example, elongation at break to be measured, and according to national standard GB/T16716.7-
2012 standards carry out biological compost degradation experiment to above-mentioned material, and the result is shown in shown in table one:
The test result of one embodiment 1-4 of table, 1 material of comparative example
| Tensile strength/MPa | Elongation at break/% | 6 months compost degradation rate % | |
| Embodiment 1 | 20 | 311 | 98 |
| Embodiment 2 | 24 | 301 | 98 |
| Embodiment 3 | 27 | 308 | 98 |
| Embodiment 4 | 30 | 302 | 97 |
| Comparative example 1 | 17 | 300 | 98 |
From in upper table one using test result it can be seen that with the non-modified poly- hydroxy aliphatic of degradable material starch base
Acid esters ester (PHA) comparative example 1 is compared, by the Examples 1 to 4 of lignin modification in the case where degradation property is basically unchanged,
There is promotion in mechanical property by the PHA of lignin modification, tensile strength has obtained significantly enhancing, wherein with wooden
The increase of cellulose content, this enhancing is more and more obvious, simultaneously because the increase of content of lignin, the finished product of product constantly under
Drop, the above comparison can show advantage of the invention.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of lignin modification starch base PHA biodegrade membrane material, which is characterized in that including walking as follows
It is rapid:
(1) by starch base polyhydroxyalkanoate (PHA) particle, lignin respectively into vacuum drying；
(2) be added in high mixer it is dry after starch base polyhydroxyalkanoate (PHA) particle, lignin and chain extender,
Antioxidant, plasticizer, lubricant, heat stabilizer are uniformly mixed, and mixed material is made；
(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization, lignin-starch base PHA composite plastic is made
Grain；
(4) the composite plastic grain is subjected to blown film at a certain temperature, prepares lignin modification starch base PHA biodegrade membrane material
Material.
2. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
According to parts by weight, each raw material dosage proportion is as follows:
3. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (1), content of starch is 20-35% in starch base polyhydroxyalkanoate (PHA) particle.
4. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (1), lignin is original powder, and particle size range is 100~800 mesh.
5. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (1), drying temperature is 25~40 degrees Celsius, and drying time is 1.5h~3h, and vacuum degree is 0~5000Pa
(absolute pressure).
6. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (2), heat stabilizer is one of maleic anhydride, epoxidized soybean oil；Lubricant be calcium stearate,
In zinc stearate or any one of oleamide series lubricant agent or two kinds or more mixtures；Plasticizer is three fourth of citric acid
Ester, triethyl citrate, any one of acetyl tri-n-butyl citrate, triacetyl glycerine, dibutyl sebacate or two kinds
Above compound.
7. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (2), antioxidant is butylated hydroxy anisole, dibutyl hydroxy toluene, butyl to biphenol, phosphorous acid
Benzene diisodecyl ester, pentaerythritol bis-phosphite, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionate, phosphorous
One of sour three (2,4- di-tert-butyl-phenyl) esters, 3,5- di-tert-butyl-hydroxy phenyl propionic acid, ten caprylate or two
Kind or more compound；Chain extender is hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, ethylene glycol, 1,4-
One of butanediol, 1,6-HD, diethylene glycol or two or more compounds.
8. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (3), extrusion temperature is 150~200 DEG C.
9. the preparation method of lignin modification starch base PHA biodegrade membrane material according to claim 1, feature exist
In in the step (4), blown film temperature is 140~180 DEG C.
10. a kind of lignin modification starch base PHA biodegrade membrane material prepared such as any one of claim 1-9 the method
Material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021163778A1 (en) | 2020-02-18 | 2021-08-26 | Biopolix Materiais Tecnológicos Ltda - Me | Biodegradable, thermoplastic, nanostructured bioresin composition, bioresin obtained and article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114896A (en) * | 2000-08-01 | 2002-04-16 | Nippon Paper Industries Co Ltd | Lignin-based resin composition |
| CN102070891A (en) * | 2010-12-24 | 2011-05-25 | 中科院广州化学有限公司 | Polyester composite filled with lignin and preparation method thereof |
| CN106589871A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified PHA biodegradable plastic and preparing method thereof |
-
2017
- 2017-05-18 CN CN201710353050.1A patent/CN108948691A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114896A (en) * | 2000-08-01 | 2002-04-16 | Nippon Paper Industries Co Ltd | Lignin-based resin composition |
| CN102070891A (en) * | 2010-12-24 | 2011-05-25 | 中科院广州化学有限公司 | Polyester composite filled with lignin and preparation method thereof |
| CN106589871A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified PHA biodegradable plastic and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021163778A1 (en) | 2020-02-18 | 2021-08-26 | Biopolix Materiais Tecnológicos Ltda - Me | Biodegradable, thermoplastic, nanostructured bioresin composition, bioresin obtained and article |
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Application publication date: 20181207 |