CN106700460B - A kind of lignin modification PCL biodegradable plastic and preparation method thereof - Google Patents

A kind of lignin modification PCL biodegradable plastic and preparation method thereof Download PDF

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CN106700460B
CN106700460B CN201611193985.XA CN201611193985A CN106700460B CN 106700460 B CN106700460 B CN 106700460B CN 201611193985 A CN201611193985 A CN 201611193985A CN 106700460 B CN106700460 B CN 106700460B
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lignin
pcl
preparation
biodegradable plastic
polycaprolactone
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CN106700460A (en
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施晓旦
邵威
金霞朝
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Shanghai Changfa New Materials Co Ltd
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Jining Ming Sheng New Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of preparation methods of lignin modification PCL biodegradable plastic, comprising the following steps: (1) is dried in vacuo a certain amount of polycaprolactone, lignin;(2) addition polycaprolactone, lignin and chain extender, antioxidant, plasticizer, lubricant, heat stabilizer after drying is added in high mixer, are sufficiently mixed;(3) gained mixed material is passed through into twin-screw extrusion machine extruding pelletization;(4) gained lignin-PCL composite plastic grain is subjected to injection molding at a certain temperature, lignin modification PCL biodegradable plastic is made.The present invention using nature largely existing biomass lignin with PCL is compound prepares biodegradable plastic, while meeting degradable requirement after composite modified, the mechanical property of pure PCL resin is enhanced, and effectively reduces this kind of plastics and obtains cost, is allowed to be more advantageous to marketing.

Description

A kind of lignin modification PCL biodegradable plastic and preparation method thereof
Technical field
The present invention relates to biological plastics technical field more particularly to a kind of lignin modification PCL biodegradable plastic and its Preparation method.
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,
Polycaprolactone (PCL) is a kind of thermoplastic resin of semicrystalline, the mechanics that crystallinity is about 45% or so, PCL Performance is similar to middle density polyolefin, elongation at break and tensile strength between LDPE and HDPE, softness with Nylon is similar, and glass transition temperature is -60 DEG C, and fusing point is 63 DEG C, and decomposition temperature is about 250 DEG C.In addition PCL molecule lactones is deposited Make it that there is preferable biodegradability and PHYSIOLOGICALLY COMPATIBLE performance, can support the growth of fungi, can be used as the carbon of microorganism Source will be slow degradation in soil, and average degradation time is 12~18 months, belong to excellent biodegradable quasi polymer.PCL Melt viscosity it is very low, have good thermoplastic processability, easily molded processing, can with traditional processing technology as squeeze out, infuse The molding such as modeling, wire drawing and blown film can be made into and have excellent performance film and other packaging material PCL can be applied to medical material, packet Package material, coating material, aquatic products and agricultural field, however due to production-scale restriction, price is still tall and big in common plastics (2~8 times), make the barrier of marketing.
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 PCL biodegradable plastics and preparation method thereof.
The preparation method of lignin modification PCL biodegradable plastic of the present invention is through the invention in biodegradable material PCL On the basis of introduce biological material lignin, while degradable requirement is met after composite modified, enhance pure PCL tree The mechanical property of rouge, and effectively reduce this kind of plastics and obtain cost, it 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 method of lignin modification PCL biodegradable plastic, including Following steps:
(1) a certain amount of polycaprolactone, lignin are dried in vacuo respectively;
(2) addition polycaprolactone and lignin and chain extender, antioxidant, plasticising after drying is added in high mixer Agent, lubricant, heat stabilizer after being sufficiently mixed, obtain mixed material;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, obtains lignin-PCL composite plastic grain;
(4) gained lignin-PCL composite plastic grain is subjected to injection molding at a certain temperature, lignin modification is made PCL biodegradable plastic.
Further, polycaprolactone uses the polycaprolactone synthesized by petroleum-based feedstock route in the step (1).It is excellent Selection of land, the polycaprolactone are the polycaprolactone raw material of Shenzhen brilliance great achievement Esun1200C trade mark.
Further, lignin is original powder in the step (1), and partial size is 100~800 mesh;Its partial size is preferably 150 ~600 mesh;Preferably 200~500 mesh;More preferably 300~400 mesh.
Further, the drying process in the step (1) are as follows: drying temperature is 10~25 DEG C, drying time 1.5h ~3h, vacuum degree are 0~5000Pa (absolute pressure);Preferably, drying temperature be 12~22 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 (2), the heat stabilizer in maleic anhydride, epoxidized soybean oil one Kind;The lubricant is selected from one of calcium stearate, zinc stearate, oleamide series lubricant agent or two kinds or more mixtures; The plasticizer is selected from tributyl citrate, triethyl citrate, acetyl tri-n-butyl citrate, triacetyl glycerine, the last of the ten Heavenly stems two One of dibutyl phthalate or two kinds or more compound;The antioxidant is selected from butylated hydroxy anisole, butylated hydroxy-a Benzene, butyl are to biphenol, phosphorous acid benzene diisodecyl ester, pentaerythritol bis-phosphite, 3- (3,5- di-t-butyl -4- hydroxy benzenes Base) propionate, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3,5- di-tert-butyl-hydroxy phenyl propionic acid ten One or more of caprylate compound;The chain extender is selected from hydroquinone two hydroxy ethyl ether, resorcinol two One or more of hydroxyethyl ether, bisphenol-A, ethylene glycol, 1,4- butanediol, 1,6-HD, diethylene glycol compounding Object.
Further, the mixing temperature of high mixer described in the step (3) be 100~110 DEG C, revolving speed be 800~ 1000r/min, incorporation time are 10~20min.
Further, the extrusion temperature of double screw extruder is 70~100 DEG C in the step (3);Preferably 75~95 ℃;More preferably 80~90 DEG C.
Further, injection molding temperature is 65~120 DEG C in the step (3);Preferably 70~110 DEG C;More preferably It is 80~90 DEG C.
Further, in the preparation method of lignin modification PCL biodegradable plastic, according to parts by weight, each original Expect that consumption proportion is as follows:
Preferably, in the preparation method of lignin modification PCL biodegradable plastic, according to parts by weight, each raw material Consumption proportion is 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 modified PCL biodegrade modeling of the quality using above method preparation Material.
The third aspect of the invention is to provide a kind of modified PCL biodegradable plastic of the quality and is preparing medical material Material, packaging material, coating material, aquatic products and agricultural field, shopping bag, refuse bag, mulch, the application in greenhouse membrane material.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
The lignin original powder that method of the invention is prepared by using the biomass being widely present from nature is right PCL Biodegradable resin be modified modification be made lignin-PCL composite biological degradation plastic, can be widely used for medical material, The membrane materials such as packaging material, coating material, aquatic products and agricultural field, shopping bag, refuse bag, mulch, awning film;The quality is modified The membrane material that PCL biodegradable plastic is prepared relative to traditional pure PCL resin, can be with while equally solving white pollution The effective consumption for reducing petroleum based material (the raw material caprolactone of PCL is all made of petroleum refining), and effectively promoted The mechanical property of membrane material;Raw material of the present invention are cheap and easy to get, and preparation process is simple, easy to operate, are produced into This is low, is conducive 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 PCL biodegradable plastic of embodiment
(1) according to parts by weight, each raw material dosage proportion of use is as follows:
(2) specific preparation method, comprising the following steps:
(1) a certain amount of PCL, lignin powder (150 mesh) are dried to 2.5h under the conditions of 25 DEG C, 0~5000Pa;
(2) dried PCL, lignin powder and bisphenol-A, dibutyl hydroxy toluene, citric acid are added in high mixer Triethyl, epoxidized soybean oil, zinc stearate, control temperature of charge are 100-105 DEG C, are mixed 15 minutes, revolving speed 900r/min;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 70~75 DEG C, is made Lignin-PCL composite plastic particle;
(4) lignin-PCL composite plastic is molded into standard injection molding according to GB/T 1040.2-2006 by injection molding machine Part, control injection molding temperature are 65~75 DEG C, and various lignin modification PCL biodegradable plastic materials are made.
The preparation of 2 lignin modification PCL biodegradable plastic of embodiment
(1) according to parts by weight, each raw material dosage proportion of use is as follows:
(2) specific preparation method, comprising the following steps:
(1) a certain amount of PCL, lignin (150 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa;
(2) dried PCL, lignin and acetyl tri-n-butyl citrate, resorcinol two are added in high mixer To biphenol, epoxidized soybean oil, calcium stearate, controlling temperature of charge is 110 DEG C, is mixed 20 minutes, revolving speed for hydroxyethyl ether, butyl For 1000r/min;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 80~85 DEG C, is made Lignin-PCL composite plastic particle;
(4) lignin-PCL composite plastic is molded into standard injection molding according to GB/T 1040.2-2006 by injection molding machine Part, control injection molding temperature are 80~85 DEG C, and various lignin modification PCL biodegradable plastic materials are made.
The preparation of 3 lignin modification PCL biodegradable plastic of embodiment
(1) according to parts by weight, each raw material dosage proportion of use is as follows:
(2) specific preparation method, comprising the following steps:
(1) a certain amount of PCL, lignin (200 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa;
(2) PCL, lignin and maleic anhydride, triacetyl glycerine, butyl after drying is added in high mixer To biphenol, 1,4-butanediol, zinc stearate, controlling temperature of charge is 105 DEG C, is mixed 25 minutes, revolving speed 1000r/min;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 80~85 DEG C, is made Lignin-PCL composite plastic particle;
(4) lignin-PCL composite plastic is molded into standard injection molding according to GB/T 1040.2-2006 by injection molding machine Part, control injection molding temperature are 90~100 DEG C, and various lignin modification PCL biodegradable plastic materials are made.
The preparation of 4 lignin modification PCL biodegradable plastic of embodiment
(1) according to parts by weight, each raw material dosage proportion of use is as follows:
(2) specific preparation method, comprising the following steps:
(1) a certain amount of PCL, lignin (300 mesh) are dried to 3h under the conditions of 25 DEG C, 0~5000Pa;
(2) PCL, lignin and triacetyl glycerine, bisphenol-A, phosphorous acid benzene two after drying is added in high mixer Isodecyl ester, epoxidized soybean oil, zinc stearate, control temperature of charge are 105 DEG C, are mixed 25 minutes, revolving speed 800r/min;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, control extrusion temperature is 90~100 DEG C, system Obtain lignin-PCL composite plastic particle;
(4) lignin-PCL composite plastic is molded into standard injection molding according to GB/T 1040.2-2006 by injection molding machine Part, control injection molding temperature are 110~120 DEG C, and various lignin modification PCL biodegradable plastic materials are made.
Comparative example 1 by the trade mark of unmodified Shenzhen brilliance great achievement be Esun1200C polycaprolactone material as a comparison 1。
Performance test
Using universal electrical tensile testing machine (SUN500 type is manufactured by Italian GALDABINI company) to according to GB/T 1040.2-2006 standard above-described embodiment 1-4, tensile strength, elongation at break, the bending strength, bending die of 1 material of comparative example Amount is measured, and carries out biological compost degradation experiment to above-mentioned material according to national standard GB/T16716.7-2012 standard, specifically 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
As in above-mentioned table 1 using test result it can be seen that pure with degradable material made from non-modified comparative example 1 Polycaprolactone is compared, by the Examples 1 to 4 of the method for the present invention lignin modification in the case where degradation property is basically unchanged, There is promotion in mechanical property by the PBAT of lignin modification, tensile strength is enhanced, bending strength, bending modulus It has been significantly improved, wherein this enhancing is more and more obvious with the increase of content of lignin;Therefore, the present invention is made Lignin modification PCL biodegradable plastic while meeting degradable requirement, effectively enhance the power of pure PCL resin Performance is learned, and reduces production cost, is allowed to be more advantageous to marketing, relatively existing unmodified pure polycaprolactone has Apparent technical advantage.
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 (7)

1. a kind of preparation method of lignin modification PCL biodegradable plastic, which comprises the following steps:
(1) a certain amount of polycaprolactone, lignin are dried in vacuo respectively;
(2) be added in high mixer dried addition polycaprolactone and lignin and chain extender, antioxidant, plasticizer, Lubricant, heat stabilizer after being sufficiently mixed, obtain mixed material;
(3) gained mixed material is passed through into double screw extruder extruding pelletization, obtains lignin-PCL composite plastic grain;
(4) gained lignin-PCL composite plastic grain is subjected to injection molding at a certain temperature, it is raw that lignin modification PCL is made Object degradative plastics;
Wherein, the drying process in the step (1) are as follows: drying temperature is 10~25 DEG C, and drying time is 1.5h~3h, vacuum Degree is 0~5000Pa;
In the step (2), heat stabilizer is selected from one of maleic anhydride, epoxidized soybean oil;The lubricant is selected from One of calcium stearate, zinc stearate, oleamide series lubricant agent or two kinds or more mixtures;The plasticizer is selected from lemon One of sour tributyl, triethyl citrate, acetyl tri-n-butyl citrate, triacetyl glycerine, dibutyl sebacate or Two kinds or more compounds;The antioxidant is selected from butylated hydroxy anisole, dibutyl hydroxy toluene, butyl to biphenol, Asia Phosphoric acid benzene diisodecyl ester, pentaerythritol bis-phosphite, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionate, One of phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3,5- di-tert-butyl-hydroxy phenyl propionic acid, ten caprylate or Two or more compounds;The chain extender is selected from hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, second two One or more of alcohol, 1,4- butanediol, 1,6-HD, diethylene glycol compound;
According to parts by weight, each raw material dosage proportion is as follows:
2. preparation method according to claim 1, which is characterized in that polycaprolactone, which uses, in the step (1) passes through stone The polycaprolactone of oil base raw material route synthesis.
3. preparation method according to claim 1, which is characterized in that in the step (1) partial size of lignin be 100~ 800 mesh.
4. preparation method according to claim 1, which is characterized in that the extrusion of double screw extruder in the step (3) Temperature is 70~100 DEG C.
5. preparation method according to claim 1, which is characterized in that in the step (3) injection molding temperature be 65~ 120℃。
6. a kind of lignin modification PCL biodegradable plastic of the method according to claim 1 to 5 preparation.
7. a kind of lignin modification PCL biodegradable plastic as claimed in claim 6 prepare medical material, packaging material, Coating material, shopping bag, refuse bag, mulch, the application in greenhouse membrane material.
CN201611193985.XA 2016-12-21 2016-12-21 A kind of lignin modification PCL biodegradable plastic and preparation method thereof Active CN106700460B (en)

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CN107141826A (en) * 2017-07-05 2017-09-08 江苏旭华圣洛迪建材有限公司 A kind of degradable lignin-base composite and preparation method thereof
CN109749330A (en) * 2017-11-01 2019-05-14 丹阳博亚新材料技术服务有限公司 A kind of novel agricultural greenhouse
CN107793718A (en) * 2017-11-09 2018-03-13 上海纳米技术及应用国家工程研究中心有限公司 Medical 3D printing plastics and its application
CN107722582A (en) * 2017-11-09 2018-02-23 上海纳米技术及应用国家工程研究中心有限公司 Biodegradable plastic film master batch and its application
CN108485207A (en) * 2018-02-13 2018-09-04 南京工业大学 A kind of degradable mulch and preparation method thereof with slow-release phosphate fertilizer
CN108587095B (en) * 2018-05-15 2020-09-29 江南大学 Full-bio-based toughening polylactic acid composite material and preparation method thereof
CN112390998B (en) * 2020-11-16 2022-04-22 深圳市正旺环保新材料有限公司 Environment-friendly plastic bag and preparation method thereof

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