CN109608838A - One kind can the degradable long-acting transparent polylactic acid of toughening and preparation method thereof - Google Patents
One kind can the degradable long-acting transparent polylactic acid of toughening and preparation method thereof Download PDFInfo
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- CN109608838A CN109608838A CN201811217586.1A CN201811217586A CN109608838A CN 109608838 A CN109608838 A CN 109608838A CN 201811217586 A CN201811217586 A CN 201811217586A CN 109608838 A CN109608838 A CN 109608838A
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- polylactic acid
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- plasticizer
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- degradable
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of biodegradable transparent plasticizing polylactic acids and preparation method thereof.The material includes polylactic acid, isocyanates chain extender, ethylene-vinyl acetate copolymer, plasticizer, organic nucleating agent, and above-mentioned plasticizer includes polyethylene glycol, polypropylene glycol.The present invention guarantees polylactic acid original transparent performance while increasing substantially toughness and heat resistance, and this material has completely biodegradable energy, toughness of material can be improved by the ratio of the distribution of regulatory molecule amount and high molecular weight component, the plasticizer compounding of different molecular weight and chain extension in situ greatly reduce migration.Implementation method is relatively simple, and material is packed suitable for transparent blister, and transparency and heat-proof cutlery box etc. expands the application field of polylactic acid.
Description
Technical field
The present invention relates to biodegradable polylactic acid material modification field, in particular to a kind of transparent plasticizing polylactic acid and its system
Preparation Method.
Background technique
High molecular material is that the development of human society is made that tremendous contribution, varied especially in nearly 100 years
High molecular material be dissolved into us and each of live details, keep our life more and more convenient, fast.However it is a large amount of
Petroleum based material difficult to degrade use, not only consume our petroleum resources, also bring great burden to environment.Biology can
Degradable material can then be fully solved both of these problems, thus biology base high molecular material more and more paid close attention to by people and
Research.
It is raw material by life that polylactic acid (PLA), which is by the starch extracted in reproducible plant resources (such as corn, cassava),
Object fermentation is prepared.Its product after discarded can quickly by microorganism it is degradable be carbon dioxide and water, will not be to ring
It causes to bear in border.The yield of annual polylactic acid has reached 200,000 tons both at home and abroad at present, with performance constantly improve and material
The expansion of application, production capacity can also be incremented by, it is seen that its development prospect is very wide.In addition, polylactic acid have it is good the transparency and
Physical property has had mature application, such as packaging material, non-woven fabrics, field of medicaments etc. in many fields.But it is poly-
The brittleness of lactic acid itself is larger, and heat resistance is bad, limits the application of polylactic acid.
More modification is carried out to polylactic acid to expand the application field of polylactic acid, many scholars and research staff to grind
Study carefully.But can studying in terms of degradable transparent plasticizing polylactic acid and few.Wherein application No. is 201310101844
Chinese patent literature discloses a kind of method for preparing complete biodegradable plasticized poly lactic acid, by polyadipate diethylene glycol (DEG) ester and gathers
Lactic acid melt blending is prepared, the degradation property and the transparency of the certifiable material of this method, but polyadipate diethylene glycol (DEG) ester number
Lattice are expensive, and the preparation cost of material is higher, can not be mass produced.It is public in the Chinese patent application No. is 201610121527
It opens and polylactic acid and polyadipate/butylene terephthalate is blended, toughness sacrifices the transparency of polylactic acid while raising.
Chinese patent 201010618280 discloses tributyl citrate and hexamethylene -1,2- dicarboxyl dinonyl plasticized poly lactic acid
Method, the elongation at break of material reach 325%, but since small molecule plasticizer is added excessively, it can be because biggish in the later period
Migration abjection leads to the decline of performance.Ethylene-vinyl acetate copolymer price is lower in the present invention, and transparency is high, degradability
Can be good, the material of preparation has high fondant-strength and good toughness, the expansion and difference point of the distribution of polylactic acid molecule amount
Being used cooperatively for son amount plasticizer inhibits migration of plasticizer and rear crystallization.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind can degradable transparent plasticizing polylactic acid and its preparation side
Method, obtained mixture have fully biodegradable, high impact and the high grade of transparency, can satisfy transparent packaging material with
And the requirement of disposable transparent tableware, and preparation method is simple, it is at low cost, it can be achieved that large-scale industrial production.
Present invention firstly provides one kind can degradable transparent plasticizing polylactic acid material, material each component is according to parts by weight
It include: 60-85 parts of polylactic acid, 5-20 parts of ethylene-vinyl acetate copolymer, 5-15 parts of plasticizer, 0-1.5 parts of chain extender, at
0-3 parts of core agent.
Preferably, the weight average molecular weight of the polylactic acid is 90000-180000g/mol.
Preferably, the weight average molecular weight of the ethylene-vinyl acetate copolymer is 200000-600000g/mol.
Preferably, the weight average molecular weight of the plasticizer polyethylene glycol is 400-6000g/mol, the weight of polypropylene glycol
Average molecular weight is 400-6000g/mol.
Preferably, the nucleating agent is hydrazide kind compound, the one or two of TMC-300 and TMC-306.
Preferably, the chain extender is hexamethylene diisocyanate, methyl diphenylene diisocyanate, different fluorine that
The one or more of ketone diisocyanate.
One kind according to claim 1 can degradable transparent plasticizing polylactic acid preparation method, it is characterised in that:
Ethylene-vinyl acetate copolymer, nucleating agent, antioxidant is added after polylactic acid, plasticizer, chain extender are mixed, is mixed
Object obtains polylactic resin by said mixture in 150 DEG C of -190 DEG C of blending extrusions, and material each component wraps according to parts by weight
It includes: 60-85 parts of polylactic acid, 5-20 parts of ethylene-vinyl acetate copolymer, 5-15 parts of plasticizer, 0-1.5 parts of chain extender, nucleation
0-3 parts of agent.
Above-mentioned melt blending is granulated using double screw extruder, and wherein each section of extruder of temperature is set as 150
DEG C, 160 DEG C, 180 DEG C, 190 DEG C, 190 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C.Screw speed is in 150-350rpm/min.
After the present invention mixes polylactic acid, ethylene-vinyl acetate copolymer, plasticizer, chain extender, squeezed by twin-screw
Machine melt pelletization obtains transparent toughening high heat resistance poly-lactic acid material that can be degradable out, has very excellent performance, especially
The brittleness for significantly improving polylactic acid, improves impact strength and elongation at break, and material can be widely applied to transparent
In blister package and heat-resisting transparent cutlery box, and then expand the application range of poly-lactic acid material.
By the present invention in that use can be degradable transparent vinyl-vinyl acetate co-polymer as toughener, itself
Degradability make be blended after material be still degradable material.Pass through the distribution of allotment polylactic acid molecule amount and control macromolecule
Amount constituent content improves the toughness of material, drastically reduces the additive amount of small molecule plasticizer, the high transparency of polylactic acid
Degree is also maintained；And it is connect in situ by using the polyethylene glycol of different molecular weight and polypropylene glycol compounding and when being blended
Branch chain extension, increases the effect of plasticizer molecule and polylactic acid molecule, migration of plasticizer is inhibited, and makes polyethylene glycol
Rear crystallization can be greatly reduced, thus reduce because high molecular weight polyethylene glycol crystallize bring problem of phase separation.Compared to mesh
The preceding biggish polylactic resin of brittleness, poly-lactic acid material impact strength provided by the invention reach 25KJ/m2, elongation at break can
Up to 316%, melt strength obtains larger raising, and the modulus of material and tensile strength are too many there is no losing, and final material is complete
Full up foot application requirement.
Specific embodiment
In order to which the present invention can be better understood, further the present invention is elaborated.
Transparent plasticizing polylactic acid material of the invention includes: 60-85 parts of polylactic acid according to parts by weight, ethyl vinyl acetate
5-20 parts of vinyl ester copolymers, 5-15 parts of plasticizer, 0-1.5 parts of chain extender, 0-3 parts of nucleating agent.
60-85 parts of polylactic acid, at 190 DEG C of environment temperature, when load is 2.16Kg, the melt index of the polylactic acid is
(2-25) g/10min, controls molecular weight distribution and polylactic acid high molecular weight component, and the toughness of material improves；
5-20 parts of ethylene-vinyl acetate copolymer, the degradable ethylene-vinyl acetate copolymer Weight-average molecular
200000-600000g/mol is measured, is transparent grain.
5-15 parts of plasticizer, it includes polyethylene glycol that the plasticizer, which is non-toxic, environmental friendly plasticizer, and weight average molecular weight is
200-6000g/mol；Molecular weight is less than or equal to be liquid under room temperature when 1000g/mol, is solid-state under remaining room temperature；Polypropylene glycol
Weight average molecular weight be 400-6000g/mol, be thick liquid under room temperature, compounded using the plasticizer of high low molecular weight,
It can also inhibit migration of plasticizer and rear crystallization behavior while improving plasticization effect；
The nucleating agent is hydrazide kind compound, and the one or two of TMC-300 and TMC-306 can be significantly
The flexible chain for reducing polylactic acid makes it quickly form small spherocrystal, and final material obtains higher crystallinity, and heat resistance obtains
Improve and does not influence the transparency.
Chain extender is isocyanate ester compound, can be reacted with hydroxyl, is used for chain extension plasticizer herein, and decrease is moved
It moves plasticization effect caused by effect to decline, and inhibits the rear crystallization of high molecular weight polyethylene glycol, prevent it from mutually separating with polylactic acid；
It also include necessary antioxidant and lubricant in the present invention, degradation when antioxidant prevents material at high temperature from processing,
Lubricant can weaken interior external friction when processing.
Embodiment is as follows:
The molecular weight of L130 is 100000g/mol in above embodiments, and the molecular weight of L175 is 170000g/mol.
The above required material is weighed after mixing according to weight percent, is put into the extruder that temperature is set as required,
It is after granulation that particle is 8 hours dry in 60 DEG C of vacuum desiccators.
After the molding of the above various embodiments poly-lactic acid material, according to the tensile strength of GB/T1040.2 measurement material, foundation
GB/T 9431 tests impact strength, and GB/T 1634.1-2 tests heat distortion temperature, and GB/T 19658 tests light transmittance and mist
Angle value.
Table 1: the test result of embodiment
By above-mentioned experimental result it is found that the toughness of poly-lactic acid material provided by the invention fully meets general packing timber
The requirement of material and medical material, impact strength is up to 25KJ/m2, elongation at break reaches 316%, and heat distortion temperature exists
110 DEG C, light transmittance reaches 90%, and the transparency of material is not substantially reduced, and heat resistance is also improved, more valuable
It is that ethylene-vinyl acetate copolymer of the invention has good degradation property, the range that usage amount is required in degradable material
It is interior, by being used in compounding the PLA of different molecular weight, and the use ratio of guarantee high molecular weight PLA, molecular weight point can be expanded
Cloth improves the toughness of polylactic acid.The compounding and chain extension of plasticizer are improved property retention rate, disposably solve poly- cream
The heat-resisting technical barrier of the transparent toughening of acid, has very strong practicability.
Above embodiments are merely used to help understand the thought of technical method and its core of the invention.But it should manage
Solution, these examples are only illustrative of the invention and is not intended to limit the scope of the invention.It is reading in set forth in the present invention
After appearance, relevant technical staff in the field can make simple change to the present invention, should be construed as being included within the present invention.
Claims (7)
1. one kind can degradable transparent plasticizing polylactic acid, component includes: polylactic acid, ethylene-vinyl acetate copolymer, increasing
Mould agent, chain extender and nucleating agent, it is characterised in that material each component is according to parts by weight, comprising: 60-85 parts of polylactic acid, ethylene-
5-20 parts of vinyl acetate co-polymer, 5-15 parts of plasticizer, 0-1.5 parts of chain extender, 0-1.5 parts of nucleating agent.
2. one kind according to claim 1 can degradable transparent plasticizing polylactic acid, it is characterised in that the polylactic acid
Weight average molecular weight is between 90000-180000g/mol, including high molecular weight PLA and low molecular weight PLA.
3. one kind according to claim 1 can degradable transparent plasticizing polylactic acid, it is characterised in that the toughener
It is degradable transparent toughener ethylene-vinyl acetate copolymer.
4. one kind according to claim 1 can degradable transparent plasticizing polylactic acid, it is characterised in that: the plasticizer
It is the one or two of polyethylene glycol, polypropylene glycol, wherein the molecular weight of polyethylene glycol is between 200-6000g/mol, and poly- third
The molecular weight of glycol is in 400-5000g/mol.
5. one kind according to claim 3 can degradable transparent plasticizing polylactic acid, it is characterised in that pass through regulatory molecule
The ratio of amount distribution and high molecular weight moieties by being used in compounding the PLA of different molecular weight, and guarantees high molecular weight PLA's
High use ratio can expand molecular weight distribution, improve the toughness of polylactic acid.
6. one kind according to claim 5 can degradable transparent plasticizing polylactic acid, it is characterised in that: the polylactic acid
Impact strength is greater than 14KJ/m2, elongation at break reaches 70% or more, and for heat distortion temperature at 110 DEG C or more, light transmittance reaches 86%
More than.
7. it include being used in compounding the plasticizer of different molecular weight in the application method of plasticizer according to claim 6,
And chain extender is added, it further suppresses migration of plasticizer and is precipitated and rear crystalline polamer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811217586.1A CN109608838A (en) | 2018-10-18 | 2018-10-18 | One kind can the degradable long-acting transparent polylactic acid of toughening and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811217586.1A CN109608838A (en) | 2018-10-18 | 2018-10-18 | One kind can the degradable long-acting transparent polylactic acid of toughening and preparation method thereof |
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| CN109608838A true CN109608838A (en) | 2019-04-12 |
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| CN201811217586.1A Pending CN109608838A (en) | 2018-10-18 | 2018-10-18 | One kind can the degradable long-acting transparent polylactic acid of toughening and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363174A (en) * | 2020-03-31 | 2020-07-03 | 宁波普莱斯帝金属制品有限公司 | Preparation method of starch/polycaprolactone composite material |
| CN112592600A (en) * | 2020-12-30 | 2021-04-02 | 滁州吉胜新材料科技有限公司 | Degradable disposable lunch box |
| CN113337092A (en) * | 2021-06-16 | 2021-09-03 | 西华大学 | Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602219A (en) * | 2016-03-28 | 2016-05-25 | 东莞市恒丰高新技术开发有限公司 | Biodegradable polylactic acid modified material |
| CN106519618A (en) * | 2016-11-23 | 2017-03-22 | 吉林中粮生化有限公司 | High-polylactic acid-content film and preparation method thereof |
-
2018
- 2018-10-18 CN CN201811217586.1A patent/CN109608838A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602219A (en) * | 2016-03-28 | 2016-05-25 | 东莞市恒丰高新技术开发有限公司 | Biodegradable polylactic acid modified material |
| CN106519618A (en) * | 2016-11-23 | 2017-03-22 | 吉林中粮生化有限公司 | High-polylactic acid-content film and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363174A (en) * | 2020-03-31 | 2020-07-03 | 宁波普莱斯帝金属制品有限公司 | Preparation method of starch/polycaprolactone composite material |
| CN111363174B (en) * | 2020-03-31 | 2022-08-09 | 宁波普莱斯帝金属制品有限公司 | Preparation method of starch/polycaprolactone composite material |
| CN112592600A (en) * | 2020-12-30 | 2021-04-02 | 滁州吉胜新材料科技有限公司 | Degradable disposable lunch box |
| CN113337092A (en) * | 2021-06-16 | 2021-09-03 | 西华大学 | Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof |
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Application publication date: 20190412 |
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