CN106916424A - A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof - Google Patents

A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof Download PDF

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Publication number
CN106916424A
CN106916424A CN201710222593.XA CN201710222593A CN106916424A CN 106916424 A CN106916424 A CN 106916424A CN 201710222593 A CN201710222593 A CN 201710222593A CN 106916424 A CN106916424 A CN 106916424A
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pla
polylactic acid
resistant type
type full
biodegradable polylactic
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邹国享
屈鑫
赵彩霞
吴蓉
李锦春
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Changzhou University
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Changzhou University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • 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)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof, belong to the modified field of processing of high molecular material.Carry out as follows：It is technical grade PLA, dextrorotation PLA, poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）, by special twin-screw extrusion melt blending, extruding pelletization, extrusion temperature is 160 195 DEG C for ester, a small amount of chain extender.Extruder is improved, primarily to strengthening mixing intensity of the screw rod in molten section, the shearing of screw rod back segment is reduced.This method may be such that the crystalline rate of PLA is substantially improved, and increase its crystallinity, refine the crystallite dimension of PLA, shorten the molding cycle of PLA, improve its dimensional stability and heat resistance, and improve the mechanical property of polylactic acid article.The high tenacity full-biodegradable polylactic acid material prepared by this method has high intensity, high tenacity and high-fire resistance energy, and method is simple.

Description

A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof
Technical field
The present invention is a kind of high tenacity full-biodegradable polylactic acid material and preparation method thereof, belongs to processing of high molecular material Modified field.
Background technology
PLA (PLA) is a kind of important lactic acid derivative, and it with lactic acid is monomer through chemical synthesis or biosynthesis to be The family macromolecule material for obtaining, it is nontoxic nonirritant, with excellent biocompatibility, can be plastic by biological decomposition and absorption Property strong, easy processing shaping.It easily by the enzyme catabolism in the multiple-microorganism or animal and plant body in nature, ultimately forms water And carbon dioxide, it is free from environmental pollution, thus be considered as one of most promising biodegradable macromolecular material.It is maximum Advantage be recyclability and degradability.Recyclability causes that its production does not rely on oil, will not be with oil price Undue fluctuation so that PLA industry has the good capability of sustainable development；And degradability then ensure that PLA is a kind of Environment-friendly material, can slow down the white pollution problems that current plastic products are brought, therefore the research of poly-lactic acid material is subject to The extensive concern of industrial circle.
Although poly-lactic acid material has good moulding processability, polylactic acid molecule chain flexibility is poor, locomitivity It is weaker, therefore process molecular chain orientation in the presence of shearing is difficult to release, although so polylactic acid article intensity is higher, But toughness is poor, product is more crisp, easy to crack.And because polylactic acid crystal degree is low so that its heat resisting temperature only has 60 DEG C.
In order to improve the toughness of polylactic acid article, its application field is widened, different elastomers is commonly used to common with PLA Mixed, the elastomer that primarily now can be used for toughness reinforcing has：Biodegradable polyester, copolyesters, core-shell copolymerized thing, butyl acrylate-the third Olefin(e) acid ethyl ester-GMA terpolymer etc..But with the addition of toughener, the intensity of poly-lactic acid material Decline therewith, particularly when the consumption of toughener is more than 30%, the tensile strength of poly-lactic acid material can decline to a great extent.Patent CN104559097A improves the toughness of PLA with lactic acid-binary acid divalent alcohol copolymers as toughener, and addition is 5- 20wt%, but with the increase of lactic acid-binary acid divalent alcohol copolymers consumption, the elongation at break of material while increasing its Tensile strength quickly falls to 30MPa or so, and lactic acid-binary acid divalent alcohol copolymers are not at present industrialized product. Patent CN102942772A is prepared for a kind of core-shell copolymerized thing for toughener, and it by BS is core, first that it is Base methyl acrylate is the core shell structure copolymer of shell with glycidyl methacrylate copolymer.But PLA after toughness reinforcing When elongation at break reaches 200%, its tensile strength has dropped to 40MPa, and this core shell structure copolymer is not to give birth to completely The material of thing degraded, therefore the degradation capability of PLA can be influenceed.Patent CN105315632A is prepared for one kind with terephthaldehyde Sour glycol ester is the copolyesters of matrix, and improves the toughness of PLA with this copolyesters as toughening modifying, but modified The elongation at break of poly-lactic acid material is only 50%, and toughness is still poor.
In sum, the toughener part that plasticizing polylactic acid is used in patent disclosed in the past is that nondegradable have Machine thing or toughening effect are less good, and this will cause the environment friendly of poly-lactic acid material to decline；Or its is strong after toughening modifying Degree can decline to a great extent, and limit purposes.Disclosed in this invention is a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material And preparation method thereof.
The content of the invention
Present invention solves the technical problem that be that a kind of preparation method of the plasticizing polylactic acid with good result is provided,
The invention provides a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material, by the raw material of following parts by weight Composition：
Wherein described chain extender is ethylene-methyl acrylate-glyceryl methacrylate
Wherein described dextrorotation polylactic acid molecule amount is 4000-7000g/mol.
A kind of preparation method of above-mentioned plasticizing polylactic acid, is carried out in accordance with the following steps：By PLA, dextrorotation PLA, Poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester, chain extender are squeezed by special twin-screw extrusion melt blending Go out granulation, extrusion temperature is 160-195 DEG C.
The extruder mainly strengthens mixing intensity of the screw rod in melt zone by improvement, reduces cutting for screw rod back segment Shearing stress.This method may be such that the crystalline rate of PLA is substantially improved, and increase its crystallinity, refine the crystal grain chi of PLA It is very little, its dimensional stability and heat resistance are improved, and improve the mechanical property of polylactic acid article.With the increasing prepared by the method Tough PLA still possesses complete biodegradable characteristic so that the plasticizing polylactic acid is more attractive.
Temperature is 160-195 DEG C when being extruded in twin-screw, uses a special extruder, the shearing of screw rod Element mainly strengthens mixing intensity of the screw rod in molten section by reconfiguring, and reduces the shearing of screw rod back segment.
Beneficial effects of the present invention：
By PLA, PDLA and PBAT blending, both possessed the high tenacity of PBAT, but also with the high intensity of PLA, while not damaging Two kinds of degradation characteristics of material.Compared with prior art, the present invention is adding PBAT to improve PLA toughness, while also adding PDLA To improve the intensity and heat resistance of PLA.The present invention adds the PBAT of the PDLA and 25-30% of 15-20% with PLA as matrix, The temperature of extruder is set as 160-195 DEG C, in first three section of extruder, when temperature of charge is less than 185 DEG C, PLA, PDLA and PBAT is homogenous plasticized, and is well mixed in the presence of Strong shear, and when temperature of charge reaches 190-195 DEG C, PLA and PDLA exists Stereocomplex crystal (SC crystal) is formed in situ in the presence of weak shearing field, the melt temperature of this SC crystal being formed in situ is More than 220 DEG C；This SC crystal being formed in situ is the good nucleators of PLA, can improve the crystallinity of PLA, therefore in material Total crystallinity can reach 30%-40%, and this can improve the heat resistance of material；And have neither part nor lot in the part PLA chains to form crystal Then there is chain extending reaction in section and PDLA segments, SC crystal can form a good physical crosslinking in the presence of chain extender with PBAT Point, therefore can assign material good tensile property；And the content of PBAT then ensure that material more than 25% in intermingling material Good toughness；Also there are two advantages from the relatively low PDLA of molecular weight, one is that the production cost of the low PDLA of molecular weight is far below The production cost of HMW PDLA, another benefit is that in the case of identical addition, the low PDLA's of molecular weight rubs Your number is more, and the locomitivity of strand is stronger, can form more SC crystal, be conducive to improving material heat resistance and Tensile strength.
Specific embodiment
The invention provides a kind of preparation method of plasticizing polylactic acid, carry out as follows：Technical grade PLA 50-60 Part, 15-20 parts of dextrorotation PLA, poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester 25-30 parts, a small amount of chain extender By special twin-screw extrusion melt blending, extruding pelletization, extrusion temperature is 160-195 DEG C, extrusion used in the present invention Machine adjusts the position of shearing elements, i.e., set Strong shear element twice in melting zone, improves mixed effect, improves PDLA in PLA Dispersiveness in matrix；Simultaneously in homogenizing zone completely without shearing elements, using it is a kind of be similar to plunger by the way of, to reduce Change the shearing of section, promote the formation of SC crystal.The screw diameter of extruder used is 35mm, and draw ratio is 48.
With reference to each embodiment describe in detail the present invention, it is to be understood that for embodiment be intended merely to explain this hair It is bright, and be not intended to limit the scope of the present invention.
Embodiment 1
By dried technical grade PLA (trade name:NatureWorks PLA4032D, similarly hereinafter) 5kg, molecular weight are 7000g/mol dextrorotation PLAs 2kg, poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester 3kg and ethylene-acrylic acid Methyl esters-GMA 10g is granulated after being well mixed in high-speed mixer with double screw extruder, extruder Temperature control totally 10th area, extruder rotating speed is 200rpm, Temperature Distribution such as following table：
One area 2nd area 3rd area 4th area 5th area 6th area 7th area 8th area 9th area Head
Temperature 160℃ 160℃ 180℃ 190℃ 190℃ 195℃ 195℃ 195℃ 195℃ 195℃
After the particle drying of extrusion GB batten, test performance will be injected into injection (mo(u)lding) machine.Injector temperature is divided into Four sections, be respectively 160 DEG C, 190 DEG C, 200 DEG C and 195 DEG C, and mould temperature is 100 DEG C during injection moulding, and the dwell time is 20s.
Embodiment 2
By dried technical grade PLA (trade name:NatureWorks PLA4032D, similarly hereinafter) 6kg, molecular weight are 4000g/mol dextrorotation PLAs 1.5kg, poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester 2.5kg and ethene-the third E pioic acid methyl ester-GMA 25g is granulated after being well mixed in high-speed mixer with double screw extruder, is squeezed Out-of-machine temperature controls totally 10th area, and extruder rotating speed is 200rpm, Temperature Distribution such as following table：
One area 2nd area 3rd area 4th area 5th area 6th area 7th area 8th area 9th area Head
Temperature 160℃ 160℃ 180℃ 190℃ 190℃ 195℃ 195℃ 195℃ 195℃ 195℃
After the particle drying of extrusion GB batten, test performance will be injected into injection (mo(u)lding) machine.The particle that will be extruded dries After dry GB batten, test performance are injected into injection (mo(u)lding) machine.Injector temperature is divided into four sections, be respectively 160 DEG C, 190 DEG C, 200 DEG C and 195 DEG C, mould temperature is 100 DEG C during injection moulding, and the dwell time is 20s.
Embodiment 3
By dried technical grade PLA (trade name:NatureWorks PLA4032D, similarly hereinafter) 5kg, molecular weight are The dextrorotation PLA 2kg of 4000g/mol, poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester 3kg and ethylene-propylene Sour methyl esters-GMA 25g is granulated after being well mixed in high-speed mixer with double screw extruder, extrusion Machine temperature control totally 10th area, extruder rotating speed is 200rpm, Temperature Distribution such as following table：
One area 2nd area 3rd area 4th area 5th area 6th area 7th area 8th area 9th area Head
Temperature 160℃ 160℃ 180℃ 190℃ 190℃ 195℃ 195℃ 195℃ 195℃ 195℃
After the particle drying of extrusion GB batten, test performance will be injected into injection (mo(u)lding) machine.Injector temperature is divided into Four sections, be respectively 160 DEG C, 190 DEG C, 200 DEG C and 195 DEG C, and mould temperature is 100 DEG C during injection moulding, and the dwell time is 20s.
The properties of sample test result of embodiment 1-3 and comparative example 1 such as table 1.
*CN104559097A。
Comparative example 1*
PLA, homemade copolyester elastomer are carried out into melt blending in Haake banbury, blending temperature is 200 ℃.Banbury rotating speed is 70rpm, and time 9min is blended.Sample after blending is directly cooled down under air at room temperature state.Will be upper Blend is stated on vulcanizing press in 190 DEG C, 10MPa depresses to the thick sheet materials of 1mm, is cut into cut-off knife after being cooled to room temperature Dumbbell shape batten, while the impact strength batten of the standard of compacting.It is that 0.25mm lacks to determine bottom radius in the middle part of batten with milling cutter Mouthful, impact strength test is carried out on cantilever-type impact strength testing machine.

Claims (5)

1. a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material, it is characterised in that by the raw material group of following parts by weight Into：
PLA 50-60 parts,
15-20 parts of dextrorotation PLA,
It is poly-（Terephthalic acid (TPA) butanediol-co- adipic acid butanediols）Ester 25-30 parts,
A small amount of 0.1-0.25 parts of chain extender.
2. a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material according to claim 1, it is characterised in that wherein Described chain extender is ethylene-methyl acrylate-glyceryl methacrylate.
3. a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material according to claim 1, it is characterised in that wherein Described dextrorotation polylactic acid molecule amount is 4000-7000 g/mol.
4. a kind of preparation method of the high-tenacity heat-resistant type full-biodegradable polylactic acid material described in claim 1, its feature exists In carrying out in accordance with the following steps：By PLA, dextrorotation PLA, it is poly-（Terephthalic acid (TPA) butanediol-co- adipic acid butanediols） , by special twin-screw extrusion melt blending, extruding pelletization, extrusion temperature is 160-195 DEG C for ester, chain extender.
5. the preparation method of a kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material according to claim 4, it is special Levy is that screw zones temperature is 160-195oC, and screw rod, in melt zone You Liangge Strong shears area, it is shallow spiral shell then to be adopted in metering section Groove, without shearing elements.
CN201710222593.XA 2017-04-07 2017-04-07 A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof Pending CN106916424A (en)

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CN110079065A (en) * 2019-04-30 2019-08-02 常州大学 A kind of high tenacity PLA/PBAT blend alloy and preparation method thereof
CN110903620A (en) * 2019-11-28 2020-03-24 华南理工大学 Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof
CN111004483A (en) * 2018-11-01 2020-04-14 江南大学 Degradable composite material and preparation method thereof
CN111154243A (en) * 2020-01-16 2020-05-15 南京大学 Bio-based compostable degradable heat-resistant film composite material and preparation method thereof
CN111733474A (en) * 2020-05-16 2020-10-02 中国科学院理化技术研究所 Full-biodegradable dental floss and preparation method thereof
CN113024822A (en) * 2021-04-15 2021-06-25 佳易容聚合物(上海)有限公司 High-activity low-residue degradable chain extender and preparation method thereof
CN113831711A (en) * 2021-10-12 2021-12-24 江南大学 High-toughness polylactic acid composition and preparation method thereof
CN114230986A (en) * 2022-01-04 2022-03-25 浙江宏仕达科技股份有限公司 Stereo composite crystal reinforced biodegradable material
CN114957943A (en) * 2021-06-11 2022-08-30 合肥工业大学 Full-biodegradable heat-resistant polylactic acid material and preparation method thereof
CN115028976A (en) * 2022-06-07 2022-09-09 杭州德泓科技有限公司 Stereo composite interface compatibilization polylactic acid blending material and preparation method thereof
CN115322415A (en) * 2022-08-09 2022-11-11 汕头东风印刷股份有限公司 Biaxially oriented polylactic acid film and preparation method thereof

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CN111004483A (en) * 2018-11-01 2020-04-14 江南大学 Degradable composite material and preparation method thereof
CN110079065B (en) * 2019-04-30 2021-05-25 常州大学 High-toughness PLA/PBAT (poly lactic acid/poly (butylene adipate-co-terephthalate)) blend alloy and preparation method thereof
CN110079065A (en) * 2019-04-30 2019-08-02 常州大学 A kind of high tenacity PLA/PBAT blend alloy and preparation method thereof
CN110041677A (en) * 2019-04-30 2019-07-23 常州大学 A kind of complete biodegradable crosslinking polylactic acid base thermoplastic elastomer and preparation method thereof
CN110903620A (en) * 2019-11-28 2020-03-24 华南理工大学 Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof
CN110903620B (en) * 2019-11-28 2021-08-10 华南理工大学 Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof
CN111154243A (en) * 2020-01-16 2020-05-15 南京大学 Bio-based compostable degradable heat-resistant film composite material and preparation method thereof
CN111733474A (en) * 2020-05-16 2020-10-02 中国科学院理化技术研究所 Full-biodegradable dental floss and preparation method thereof
CN113024822A (en) * 2021-04-15 2021-06-25 佳易容聚合物(上海)有限公司 High-activity low-residue degradable chain extender and preparation method thereof
CN113024822B (en) * 2021-04-15 2022-05-31 佳易容聚合物(上海)有限公司 High-activity low-residue degradable chain extender and preparation method thereof
CN114957943A (en) * 2021-06-11 2022-08-30 合肥工业大学 Full-biodegradable heat-resistant polylactic acid material and preparation method thereof
CN114957943B (en) * 2021-06-11 2024-03-19 合肥工业大学 Full-biodegradation heat-resistant polylactic acid material and preparation method thereof
CN113831711A (en) * 2021-10-12 2021-12-24 江南大学 High-toughness polylactic acid composition and preparation method thereof
CN114230986A (en) * 2022-01-04 2022-03-25 浙江宏仕达科技股份有限公司 Stereo composite crystal reinforced biodegradable material
CN115028976A (en) * 2022-06-07 2022-09-09 杭州德泓科技有限公司 Stereo composite interface compatibilization polylactic acid blending material and preparation method thereof
CN115322415A (en) * 2022-08-09 2022-11-11 汕头东风印刷股份有限公司 Biaxially oriented polylactic acid film and preparation method thereof

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