CN106589854B - A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof - Google Patents
A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof Download PDFInfo
- Publication number
- CN106589854B CN106589854B CN201611192863.9A CN201611192863A CN106589854B CN 106589854 B CN106589854 B CN 106589854B CN 201611192863 A CN201611192863 A CN 201611192863A CN 106589854 B CN106589854 B CN 106589854B
- Authority
- CN
- China
- Prior art keywords
- pbsa
- biology base
- lignin
- full biology
- 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.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a kind of preparation methods of the full biology base PBSA biodegradable plastics of lignin modification, include the following steps：(1) full biology base PBSA is synthesized；(2) full biology base PBSA, lignin are dried in vacuo respectively；(3) dried full biology base PBS, lignin and a certain amount of chain extender, antioxidant, plasticizer, lubricant, heat stabilizer are added in high mixer, is sufficiently mixed；(4) by mixed material through twin-screw extrusion machine extruding pelletization；(5) and then blown film is carried out to get the full biology base PBSA biodegradable plastics of lignin modification.The present invention is by introducing biological material lignin and meeting degradable requirement through composite modified lignin PBSA composite plastics obtained, the mechanical property of full biology base PBSA resins is enhanced simultaneously, and effectively reduce this kind of plastics and obtain cost, it is allowed to be more advantageous to marketing.
Description
Technical field
The present invention relates to biological plastics technical field more particularly to a kind of full biology base PBSA of lignin modification are biodegradable
Plastics and preparation method thereof.
Background technology
Currently, with the continuous development of national economy, the consumption figure of plastic products is constantly increasing, and synthetic plastic is producing
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 that can meet people's use demand but also meet ecological requirements seems more and more urgent and causes
The broad interest of researcher, wherein degradable resin have become the heat of research due to its degradation characteristic and economic performance
Point,
Poly- is a kind of polyester material of complete biodegradable to succinic acid/tetramethylene adipate (PBSA), in natural item
Can water and carbon dioxide be finally degraded to by enzyme dispersion metabolism in multiple-microorganism and animal and plant body under part.Poly-succinic/
Tetramethylene adipate has the characteristic of poly adipate succinic acid ester and poly butylene succinate, existing good extension simultaneously
Property and elongation at break, also have preferably heat resistance and shock resistance, substantially improve the property of original binary polyester material
Energy.
The raw material of PBSA is succinic acid, adipic acid and butanediol respectively, and although PBSA plastics are biodegradable plastics, still
From the point of view of the process units of industrialization at present, its three kinds of raw material sources are still from being extracted by petrochemical industry,
So PBSA plastics are to consume petroleum resources and produce more carbon dioxide in process of production.The meaning of bio-based plastics
Think of is that the initial source of raw material of its plastics is naturally occurring biomass resource (animal and plant resource：Straw, animal body
Deng).The low-carbon emission for following bad utilization and process of resource can be achieved.Europe has begun to require to have in plastic products certain
Bio-based content, this trend are being more and more obvious, so more and more important is just being become to the research of bio-based plastics application,
So the research and modification to biology base PBSA performances have great significance.
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 there is degradability quickly from biomass resource while under composting conditions
Can, it is a kind of following more environmentally protective material.
Invention content
The object of the present invention is to provide full biology base PBSA biodegradable plastics of a kind of lignin modification and preparation method thereof.
The preparation method of the present invention on the basis of full biology base biodegradation material PBSA by introducing biological material
Lignin while meeting degradable requirement after composite modified, enhances the mechanical property of full biology base PBSA resins, and
It effectively reduces this kind of plastics and obtains cost, be allowed to be more advantageous to marketing.
It, can be effectively by the reaction on lignin surface on microcosmic simultaneously by the synergy of various functions auxiliary agent
The functional groups of property group and PBAT polymer segments can be combined together, macroscopically can be preferable by both materials
It is merged to processability superior bio base biodegradation membrane material.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of preparation of the full biology base PBSA biodegradable plastics of lignin modification
Method includes the following steps：
(1) biology base route is used to synthesize full biology base PBSA Biodegradable resins；
(2) a certain amount of full biology base PBSA, lignin are dried in vacuo respectively；
(3) dried full biology base PBS and lignin and a certain amount of chain extender, antioxygen are added in high mixer
Agent, plasticizer, lubricant, heat stabilizer after being sufficiently mixed, obtain mixed material；
(4) gained mixed material is obtained into lignin-PBSA composite plastic grains through double screw extruder extruding pelletization；
(5) gained lignin-PBSA composite plastics grain is subjected to blown film at a certain temperature, lignin modification is made and gives birth to entirely
Object base PBSA biodegradable plastics.
In step (1), to use full biology base route to produce three kinds of raw material butanediols, adipic acid and succinic acid as monomer original
Material synthesis PBSA resins, the synthesis technology of the full biology base PBSA are：(1) by raw material biology base succinic acid, biology base oneself two
Acid, biology base butanediol and composite catalyst are added in the reaction vessel of nitrogen protection；(2) anti-in the mode of temperature programming
It answers system to be warming up to 80~120 DEG C, is beaten 15~30 minutes；(3) again in a manner of temperature programming by the reaction system after mashing
180~240 DEG C are warming up to, keeps temperature 1~4 hour, carries out esterification；(4) system after Esterification Stage is taken out true
Sky is kept for 30~120 minutes between 1000~10000Pa in 180~240 DEG C, carries out prepolymerization reaction；(5) the whole poly- stage,
In 180~240 DEG C, then the system after precondensation stage is evacuated to 80Pa hereinafter, the reaction was continued 60~300 minutes, reaction
After discharge, you can the full biology base PBSA of product.
Further, lignin is original powder in the step (2), and grain size is 100~800 mesh；Its grain size is preferably 150
~600 mesh；Preferably 200~500 mesh；More preferably 300~400 mesh.
Further, the drying process in the step (2) is：Drying temperature is 25~40 DEG C, drying time 1.5h
~3h, vacuum degree are 0~5000Pa (absolute pressure)；Preferably, drying temperature be 27~35 DEG C, drying time be 2h~
2.5h, vacuum degree are 100~3000Pa (absolute pressure)；It is further preferable that drying temperature is 30~32 DEG C, drying time is
2.3h, vacuum degree are 1000~2000Pa (absolute pressure).
Further, in the step (3), the one kind of heat stabilizer in maleic anhydride, epoxidized soybean oil；Institute
State one or two or more kinds of mixtures of the lubricant in calcium stearate, zinc stearate, oleamide series lubricant agent；The increasing
It moulds agent and is selected from tributyl citrate, triethyl citrate, acetyl tri-n-butyl citrate, triacetyl glycerine, two fourth of decanedioic acid
One or two or more kinds of compounds in ester；The antioxidant is selected from butylated hydroxy anisole, dibutyl hydroxy toluene, butyl
To biphenol, phosphorous acid benzene diisodecyl ester, pentaerythritol bis-phosphite, 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid
Pentaerythritol ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3,5- di-tert-butyl-hydroxy phenyls propionic acid, ten caprylate
One or more of compound；The chain extender be selected from hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether,
One or more of bisphenol-A, ethylene glycol, 1,4- butanediols, 1,6-HD, diethylene glycol compound.
Further, the mixing temperature of high mixer described in the step (3) be 100~110 DEG C, rotating speed be 800~
1000r/min, incorporation time are 10~20min.
Further, the extrusion temperature of double screw extruder is 120~190 DEG C in the step (4)；Preferably 130~
160℃；More preferably 140~150 DEG C.
Further, blown film temperature is 125~160 DEG C in the step (5)；Preferably 135~150 DEG C；More preferably
140~145 DEG C.
Further, in the preparation method of the full biology base PBSA biodegradable plastics of the lignin modification, by weight
Number meter, each raw material dosage proportioning are as follows：
Preferably, in the preparation method of the full biology base PBSA biodegradable plastics of the lignin modification, in parts by weight
Meter, each raw material dosage proportioning are as follows：
Further, wherein the parts by weight of each raw material are 100% calculating, actual amount according to the effective content of raw material
It need to be converted according to the actually active content of raw material.
The second aspect of the invention is to provide a kind of full biology base PBSA of the lignin modification prepared using the above method
Biodegradable plastic.
The third aspect of the invention is to provide a kind of full biology base PBSA biodegradable plastics of the lignin modification and exists
Prepare the application in biodegradable shopping bag, refuse bag, mulch, green house of vegetables film, injection molding plate, injection molding sheet material.
The present invention is had the following technical effect that compared with prior art using above-mentioned technical proposal：
The lignin original powder that the method for the present invention is prepared by using the biomass being widely present derived from nature, to giving birth to entirely
The PBSA Biodegradable resins in object base source are modified modification to be prepared into the compound full biology base biologies of lignin-PBSA
Degradative plastics can be widely used for the membrane materials such as shopping bag, refuse bag, mulch, awning film；The full biology base PBSA of the lignin modification
The membrane material that biodegradable plastic is prepared relative to traditional petroleum base PBSA resins subtracts while equally solving white pollution
The consumption of few petroleum resources and carbon emission in the process, effectively realize recycling for resource, comply fully with state-of-the-art
Environmental protection concept；Simultaneously lignin introducing further promoted biology base PBSA membrane materials mechanical property, reduce material at
This, effectively reduces marketing difficulty；And raw material of the present invention are cheap and easy to get, and preparation process is simple, behaviour
Facilitate, production cost is low, is more advantageous to marketing.
Specific implementation mode
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.
First, full biology base PBSA raw materials are synthesized according to following specific method：
(1) raw material preparation：The succinic acid of biology base route comes from Dutch Royal DSM company, biology base route oneself two
Acid and butanediol come from BASF AG；
(2) specific synthesis technology is：(1) 41.35 grams of biology base succinic acid, biology base adipic acid 30.66 are weighed respectively
Gram, 90.72 grams of biology base 1,4-butanediol, (titanium silicon mol ratio is 8 to titanium dioxide with silica composite:2) 0.41 gram, Asia
0.09 gram of 0.21 gram of triethyl phosphate and magnesium acetate are added in the three-necked flask of 250mL, wherein connecing stirring flatly, are connect flatly
Nitrogen protection, another mouth connect water knockout drum and distillation column；(2) stirring is started, heating reaction system is beaten 15 minutes to 130 degree
Afterwards；(3) 235 degree are warming up to 10 degree of heating rates per minute again, keep the thermotonus after 140 minutes, removes water knockout drum
And condenser pipe, vacuum pump interface is connected, channel of nitrogen valve is closed；(4) start to be evacuated to absolute pressure 4000Pa or so, instead
It answers 60 minutes；(5) poly- stage eventually, continue to be evacuated to absolute pressure 50Pa or so, kept for 235 degree the reaction was continued 150 minutes, i.e.,
Obtain the full biology base PBSA Biodegradable resin raw materials of product.
The preparation of 1 lignin modification PBSA biodegradable plastics of embodiment
(1) it counts in parts by weight, each raw material dosage proportioning of use is as follows：
(2) specific preparation method, includes the following steps：
(1) full biology base PBSA Biodegradable resin raw materials are synthesized according to the method described above；
(2) a certain amount of biology base PBSA, lignin powder (150 mesh) is dry under the conditions of 25 DEG C, 0~5000Pa
2.0h；
(3) be added in high mixer dried biology base PBSA, lignin powder and bisphenol-A, dibutyl hydroxy toluene,
Triethyl citrate, epoxidized soybean oil, zinc stearate, control material temperature are 100-105 DEG C, are mixed 15 minutes, rotating speed is
900r/min；
(4) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 120~130 DEG C, system
Obtain lignin-biology base PBSA composite plastic particles；
(5) this is answered into lignin-biology base PBSA composite plastics and passes through blown film, control blown film temperature is 125-130 DEG C, system
Obtain various lignin modification PBSA biodegradable plastic membrane materials.
The preparation of 2 lignin modification biology base PBSA biodegradable plastics of embodiment
(1) it counts in parts by weight, each raw material dosage proportioning of use is as follows：
(2) specific preparation method, includes the following steps：
(1) full biology base PBSA Biodegradable resin raw materials are synthesized according to the method described above；
(2) a certain amount of biology base PBSA, lignin (200 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa；
(3) dried biology base PBSA, lignin and acetyl tri-n-butyl citrate, isophthalic are added in high mixer
To biphenol, epoxidized soybean oil, calcium stearate, control material temperature is 110 DEG C, mixes 20 points for diphenol dihydroxyethyl ether, butyl
Clock, rotating speed 1000r/min；
(4) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 130~140 DEG C, system
Obtain lignin-PBSA composite plastic particles；
(5) composite plastic is passed through into blown film, control blown film temperature is 150-155 DEG C, and various lignin modifications are made
PBSA biodegradable plastic membrane materials.
The preparation of 3 lignin modification biology base PBSA biodegradable plastics of embodiment
(1) it counts in parts by weight, each raw material dosage proportioning of use is as follows：
(2) specific preparation method, includes the following steps：
(1) full biology base PBSA Biodegradable resin raw materials are synthesized according to the method described above；
(2) a certain amount of biology base PBSA, lignin (250 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa；
(3) biology base PBSA, lignin and maleic anhydride, three triacetins after drying are added in high mixer
Ester, butyl are to biphenol, 1,4-butanediol, zinc stearate, and control material temperature is 105 DEG C, is mixed 25 minutes, and rotating speed is
1000r/min；
(4) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 155~160 DEG C, system
Obtain lignin-PBSA composite plastic grains；
(5) lignin-PBSA composite plastics are passed through into blown film, control blown film temperature is 155-160 DEG C, and various wood are made
Quality is modified PBSA biodegradable plastic membrane materials.
The preparation of 4 lignin modification biology base PBSA biodegradable plastics of embodiment
(1) it counts in parts by weight, each raw material dosage proportioning of use is as follows：
(2) specific preparation method, includes the following steps：
(1) full biology base PBSA Biodegradable resin raw materials are synthesized according to the method described above；
(2) a certain amount of biology base PBSA, lignin (300 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa；
(3) biology base PBSA, lignin and triacetyl glycerine after drying, bisphenol-A, phosphorous are added in high mixer
Sour benzene diisodecyl ester, epoxidized soybean oil, zinc stearate, control material temperature are 105 DEG C, are mixed 25 minutes, rotating speed 800r/
min；
(4) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 180~190 DEG C, system
Obtain lignin-PBSA composite plastic particles；
(5) lignin-PBSA composite plastics are passed through into blown film, control blown film temperature is 155-160 DEG C, and various wood are made
Quality is modified PBSA biodegradable plastic membrane materials.
Comparative example 1 is biodegradable by the full biology base PBSA processed without lignin modification synthesized according to the method described above
Resin raw material as a comparison case 1.
Performance test
Using universal electrical tensile testing machine (SUN500 types are manufactured by Italian GALDABINI companies)；Respectively to above-mentioned
The tensile strength of 1 material of Examples 1 to 4 and comparative example, elongation at break are measured, and according to national standard GB/T16716.7-
2012 standards carry out biological compost degradation experiment to above-mentioned material, and specific testing result is as shown in table 1：
Each performance applications test data of 1 Examples 1 to 4 of table and comparative example 1
| Tensile strength/MPa | Elongation at break/% | 6 months compost degradation rate % | |
| Embodiment 1 | 34 | 554 | 99 |
| Embodiment 2 | 39 | 560 | 98 |
| Embodiment 3 | 43 | 571 | 98 |
| Embodiment 4 | 48 | 570 | 97 |
| Comparative example 1 | 26 | 552 | 99 |
It can be seen that by the application test result in above-mentioned table 1：With the non-modified pure biological poly of degradable material to benzene
Dioctyl phthalate/tetramethylene adipate (PBSA) comparative example 1 is compared, by the Examples 1 to 4 of lignin modification in degradation property base
In the case that this is constant, there are promotion, the growth rate difference of tensile strength in mechanical property by the PBSA of lignin modification
It is 30.7%, 50.0%, 65.8% and 78.5%, has obtained significantly enhancing；Wherein from above-mentioned tensile strength enhancing rate
With the increase of content of lignin, this enhancing is more and more obvious.Therefore, lignin modification biology base PBSA produced by the present invention
Biodegradable plastic effectively enhances the mechanical property of pure PBSA resins, and reduce while meeting degradable requirement
Production cost, is allowed to be more advantageous to marketing, relatively existing unmodified pure biological poly terephthalic acid (TPA)/adipic acid
Butanediol ester (PBSA) has apparent technical advantage.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by impartial conversion and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of the full biology base PBSA biodegradable plastics of lignin modification, which is characterized in that including following step
Suddenly：
(1) biology base route is used to synthesize full biology base PBSA Biodegradable resins；
(2) a certain amount of full biology base PBSA, lignin are dried in vacuo respectively；
(3) dried full biology base PBSA and lignin and a certain amount of chain extender, antioxidant, increasing are added in high mixer
Agent, lubricant, heat stabilizer are moulded, after being sufficiently mixed, obtains mixed material；
(4) gained mixed material is obtained into lignin-PBSA composite plastic grains through double screw extruder extruding pelletization；
(5) gained lignin-PBSA composite plastics grain is subjected to blown film at a certain temperature, the full biology base of lignin modification is made
PBSA biodegradable plastics.
2. preparation method according to claim 1, which is characterized in that in step (1), to be produced using full biology base route
Three kinds of raw material butanediols, adipic acid and succinic acid are that raw material monomer synthesizes PBSA resins, the synthesis work of the full biology base PBSA
Skill is：(1) raw material biology base succinic acid, biology base adipic acid, biology base butanediol and composite catalyst are added to nitrogen
In the reaction vessel of protection；(2) reaction system is warming up to 80~120 DEG C in a manner of temperature programming, is beaten 15~30 minutes；
(3) reaction system after mashing is warming up to 180~240 DEG C in a manner of temperature programming again, keeps temperature 1~4 hour, carried out
Esterification；(4) between the system after Esterification Stage being evacuated to 1000~10000Pa, in 180~240 DEG C of holdings
30~120 minutes, carry out prepolymerization reaction；(5) the whole poly- stage takes out in 180~240 DEG C, then by the system after precondensation stage
Vacuum discharges after reaction to 80Pa hereinafter, the reaction was continued 60~300 minutes, you can the full biology base PBSA of product.
3. preparation method according to claim 1, which is characterized in that in the step (2) grain size of lignin be 100~
800 mesh.
4. preparation method according to claim 1, which is characterized in that the drying process in the step (2) is：Dry temperature
Degree is 25~40 DEG C, and drying time is 1.5h~3h, and vacuum degree is 0~5000Pa.
5. preparation method according to claim 1, which is characterized in that in the step (3), the heat stabilizer is selected from suitable
One kind in anhydride maleique, epoxidized soybean oil；The lubricant is selected from calcium stearate, zinc stearate, oleamide class lubrication
One or two or more kinds of mixtures in agent；The plasticizer is selected from tributyl citrate, triethyl citrate, acetyl tributyl citrate
One or two or more kinds of compounds in tri-n-butyl, triacetyl glycerine, dibutyl sebacate；The antioxidant is selected from butyl
Hydroxyanisole, dibutyl hydroxy toluene, butyl are to biphenol, phosphorous acid benzene diisodecyl ester, pentaerythritol bis-phosphite, 3-
(3,5- di-tert-butyl-hydroxy phenyl) propionate, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3,5-, bis- uncles
One or more of ten caprylate of butyl -4- hydroxy-phenylpropionic acids compound；The chain extender is selected from hydroquinone
In dihydroxyethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, ethylene glycol, 1,4- butanediols, 1,6-HD, diethylene glycol
One or more kinds of compounds.
6. preparation method according to claim 1, which is characterized in that the extrusion of double screw extruder in the step (4)
Temperature is 120~190 DEG C.
7. preparation method according to claim 1, which is characterized in that blown film temperature is 125~160 in the step (5)
℃。
8. according to claim 1-7 any one of them preparation methods, which is characterized in that count in parts by weight, each raw material dosage
Proportioning is as follows：
9. a kind of full biology base PBSA biodegradations modeling of the lignin modification prepared such as any one of claim 1-8 the methods
Material.
10. a kind of full biology base PBSA biodegradable plastics of lignin modification as claimed in claim 9 are preparing biodegradation
Application in shopping bag, refuse bag, mulch, green house of vegetables film, injection molding sheet material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611192863.9A CN106589854B (en) | 2016-12-21 | 2016-12-21 | A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611192863.9A CN106589854B (en) | 2016-12-21 | 2016-12-21 | A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589854A CN106589854A (en) | 2017-04-26 |
| CN106589854B true CN106589854B (en) | 2018-08-21 |
Family
ID=58602419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611192863.9A Active CN106589854B (en) | 2016-12-21 | 2016-12-21 | A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589854B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727571B (en) * | 2017-04-19 | 2021-01-19 | 北京化工大学 | PBS-based modified polyester 3D printing material, preparation method and application |
| CN108948689B (en) * | 2017-05-17 | 2021-03-09 | 济宁明升新材料有限公司 | Polylactic acid-lignin composite material modified by reactive extrusion method and preparation method thereof |
| CN108948680A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBSA biodegradable plastic of starch conversion and preparation method thereof |
| CN108948679A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of lignin modification starch base PBAT biodegrade membrane material and preparation method thereof |
| CN108948681A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBAT biodegradable plastic of starch conversion and preparation method thereof |
| CN108948678A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBS biodegradable plastic of starch conversion and preparation method thereof |
| CN108948690B (en) * | 2017-05-18 | 2021-03-09 | 济宁明升新材料有限公司 | Polylactic acid-lignin-starch composite material and preparation method thereof |
| CN108485207A (en) * | 2018-02-13 | 2018-09-04 | 南京工业大学 | Fully-degradable mulching film with phosphate fertilizer slow-release effect and preparation method thereof |
| CN110734631B (en) * | 2019-11-15 | 2022-02-18 | 湖南骏泰新材料科技有限责任公司 | Lignin-based biodegradable polybutylene succinate film and preparation method thereof |
| CN112920496B (en) * | 2021-03-23 | 2021-08-24 | 平湖市金球塑料制品股份有限公司 | Production process and production equipment of environment-friendly degradable plastic shopping bag |
-
2016
- 2016-12-21 CN CN201611192863.9A patent/CN106589854B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589854A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106589854B (en) | A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof | |
| CN106589855B (en) | A kind of full biology base PBAT biodegradable plastic of lignin modification and preparation method thereof | |
| CN106832801B (en) | A kind of lignin modification PBAT biodegradable plastic and preparation method thereof | |
| CN106589871A (en) | Lignin modified PHA biodegradable plastic and preparing method thereof | |
| EP3404067B1 (en) | Plasticised biodegradable polyester film and preparation method therefor | |
| CN106700442B (en) | A kind of lignin modification PBS biodegradable plastic and preparation method thereof | |
| CN101781467B (en) | Biomass-synthetic plastic product and method for preparing same | |
| CN106700460B (en) | A kind of lignin modification PCL biodegradable plastic and preparation method thereof | |
| CN104312121B (en) | Transparent polylactic acid film of high tenacity and preparation method thereof | |
| CN113619242B (en) | Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof | |
| CN108948681A (en) | A kind of full biology base PBAT biodegradable plastic of starch conversion and preparation method thereof | |
| CN113861635A (en) | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof | |
| CN106700444B (en) | A kind of full biology base PBS biodegradable plastic of lignin modification and preparation method thereof | |
| CN108948690B (en) | Polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN112063140A (en) | Polylactic acid modified material for injection molding product and preparation method thereof | |
| CN108948678A (en) | A kind of full biology base PBS biodegradable plastic of starch conversion and preparation method thereof | |
| CN103044716A (en) | Biodegradable material and preparation method thereof | |
| CN102732043B (en) | High-strength wood-plastic composite panel and preparation method thereof | |
| CN108948679A (en) | A kind of lignin modification starch base PBAT biodegrade membrane material and preparation method thereof | |
| CN108948682A (en) | A kind of lignin modification PBAT/PLA composite film material and preparation method thereof | |
| CN113619241A (en) | Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof | |
| CN114573965B (en) | High-barrier biodegradable material and preparation method and application thereof | |
| CN109694557A (en) | A kind of degradable cover film and preparation method thereof for refuse landfill | |
| CN112063139A (en) | Polylactic acid modified material for food contact injection molding product and preparation method thereof | |
| CN108948680A (en) | A kind of full biology base PBSA biodegradable plastic of starch conversion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190114 Address after: 272100 Xiguancun, Longqiao Office, Yanzhou District, Jining City, Shandong Province (in Sun Paper Industry Park) Patentee after: Jining Mantel New Materials Co., Ltd. Address before: 272100 Industrial Park of Xinglongzhuang Town, Yanzhou District, Jining City, Shandong Province Patentee before: Jining Ming Sheng new material Co., Ltd. |