CN106189129A - A kind of PLA sheet material and preparation method thereof - Google Patents
A kind of PLA sheet material and preparation method thereof Download PDFInfo
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- CN106189129A CN106189129A CN201610534912.6A CN201610534912A CN106189129A CN 106189129 A CN106189129 A CN 106189129A CN 201610534912 A CN201610534912 A CN 201610534912A CN 106189129 A CN106189129 A CN 106189129A
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003623 enhancer Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000004611 light stabiliser Substances 0.000 claims abstract description 14
- 239000004626 polylactic acid Substances 0.000 claims description 96
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 95
- 239000010410 layer Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 13
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- -1 nucleator Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XAVQYICBBWPTFT-UHFFFAOYSA-N pentane-1,1,1,2,2-pentol Chemical compound CCCC(O)(O)C(O)(O)O XAVQYICBBWPTFT-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08L67/04—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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
- C08L2207/24—Recycled plastic recycling of old tyres and caoutchouc and addition of caoutchouc particles
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)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides PLA sheet material and preparation method thereof, this PLA sheet material uses three-layer co-extruded technique to produce, for A/B/A structure, A layer is made up of PLA resin, melt strength enhancers, light stabilizer, antioxidant, and B layer is made up of PLA resin, melt strength enhancers, nucleator, antioxidant.The alternative PVC of PLA sheet material that the present invention provides makes for smart card, have heat-resist, can the advantage such as coiling, fabrication not warpage.The method that the present invention provides is simple, it is simple to large-scale production.
Description
Technical field
The invention belongs to biodegradable thermoplastic polyester sheet technology field, more particularly, to a kind of PLA sheet material and system thereof
Preparation Method.
Background technology
Ending for the end of the year 2015, China's smart card issuance amount, more than 135, becomes the country that whole world issued volume is maximum, greatly
The development promoting national economy.The main material of these cards is polyvinyl chloride resin, owing to metal is contained in inside, it is difficult to reclaim, base
This is all dropped, and causes the biggest pollution, the environmental problem that therefore smart card brings to become current industry urgent need to solve the problem.
Polylactic acid (PLA) is a kind of novel bio-based and Biodegradable material, use reproducible plant resources (as
Semen Maydis) starch material that proposed makes.Starch material obtains glucose via saccharifying, then is sent out by glucose and certain strain
Ferment makes highly purified lactic acid, then the polylactic acid by chemical synthesis process synthesis certain molecular weight.It has good biology
Degradability, can be the most degradable by microorganism in nature after using, and ultimately generates carbon dioxide and water, no
Polluting environment, this is highly beneficial to protection environment, the environment-friendly material being well recognized as.
Owing to PLA has biological degradability, it therefore it is the preferable selection substituting PVC for making smart card.Yet with
PLA crystallization is relatively slow, causes PLA metal wire when carrying out ultrasound wave coiling to be mutually wound around, and therefore needs to solve the coiling of PLA surface and asks
Topic.Additionally due to smart card to thermostability by certain requirement, also need to improve the thermostability of PLA.
License notification number is that the patent of invention of " CN 103087483B " provides a kind of card base sandwich layer with biaxial stretch-formed
Polylactic acid sheet material and preparation method thereof.The method solves PLA sheet material by special formula system and double-axes fensile work and breaks
Split percentage elongation little, thermo-labile, not hydrolysis and the defect of aging difference.But dividing in sheet material cannot being made due to double-axes fensile work
Subchain arrangement uniformly, has internal stress, sheet material therefore can be caused when fabrication to produce stress warpage.This invention simultaneously uses nucleation
Agent combines double-axes fensile work and improves the degree of crystallinity of PLA sheet material, and then improves the thermostability of sheet material, but owing to PLA crystallizes relatively
Slowly, when carrying out ultrasound wave coiling, degree of crystallinity raising can cause coiling more difficult on the contrary.
Summary of the invention
For the shortcoming of prior art, present invention is primarily targeted at solution PLA thermostability when smart card makes
Not enough and the problem of ultrasound wave coiling difficulty, the PLA sheet material of preparation have heat-resisting good, ultrasound wave coiling can be carried out, fabrication is not stuck up
The advantages such as song.
For reaching object above, the technical solution used in the present invention is:
The present invention provides a kind of PLA sheet material, for A/B/A structure, is prepared by three-layer co-extruded technique, and A layer is by following component
Preparation: PLA resin 86-92 weight portion, melt strength enhancers 7-12 weight portion, light stabilizer 0.5-1 weight portion, antioxidant
0.5-1 weight portion.
Preferably, described PLA resin is poly-dl-lactide, and mean molecule quantity is 140,000-16 ten thousand.
Preferably, described melt strength enhancers is the star polylactic acid with four paws structure, and mean molecule quantity is 20-24
Ten thousand.
Preferably, the one during described light stabilizer is UV531, UV770.
Preferably, at least one during described antioxidant is I1010, I1076.
B layer is prepared by following component: PLA resin 83-88.5 weight portion, melt strength enhancers 9-12 weight portion, nucleation
Agent 2-4 weight portion, antioxidant 0.5-1 weight portion.
Preferably, described PLA resin is Poly-L-lactic acid, containing accounting for the golden red that gross weight 10% particle diameter is 50-80 nanometer
Stone-type titanium dioxide, mean molecule quantity is 170,000-19 ten thousand.
Preferably, described nucleator is a kind of Poly-L-lactic acid and dextrorotation polylactic acid blend, and composition mass ratio is left-handed
Polylactic acid: dextrorotation polylactic acid is equal to 55%:45%, and fusing point 245 DEG C, mean molecule quantity is 200,000-22 ten thousand.
Preferably, described melt strength enhancers is the star polylactic acid of four paws structure, and molecular weight is 260,000-28 ten thousand.
Preferably, at least one during described antioxidant is I1010, I1076.
Accordingly, the present invention also provides for a kind of PLA preparation method, comprises the following steps:
(1) by A layer, B layer by respective proportioning mix homogeneously, it is separately added into corresponding feed bin.
(2) material plastifies through respective extruder, filter filters, Melt Pump is measured, melt distribution, by multiple in mould
Close, three-roller calendar cools down, rolling, prepares the PLA sheet material with A/B/A structure.
Described extruder temperature is A layer: 155 DEG C-190 DEG C, and rotating speed is 20-40r/min;B layer: 160 DEG C-200 DEG C, turns
Speed is 20-60r/min.
Described filter temperature is A layer: 185 DEG C-190 DEG C;B layer: 190 DEG C-195 DEG C.
Described Melt Pump temperature is 185 DEG C-195 DEG C;B layer: 190 DEG C-195 DEG C.
Described mould is co-extrusion monolayer mold, and temperature is 195 DEG C-200 DEG C.
Described three-roller calendar temperature is 40-45 DEG C of upper roller, central roll 25-30 DEG C, lower roll 25-30 DEG C.
Described A layer thickness 20 microns-40 microns
Beneficial effect:
The present invention provides a kind of PLA sheet material and preparation method thereof, compared with prior art, present invention employs three-layer co-extruded
Technique preparation has the PLA sheet material of A/B/A structure, and this sheet material A layer uses poly-dl-lactide to be main material, for unformed machine
Structure, has the advantage that rate of cooling is fast, and when ultrasound wave coiling, energy melt can reach and solidify rapidly, makes metal wire be solidificated in sheet material
Surface, and the polylactic acid of undefined structure difference in functionality Coating combination when hot pressing fabrication is more firm.B layer uses left-handed poly-breast
Acid combines nucleator makes sheet material have good thermostability, it is possible to meets smart card and uses requirement.Nucleator in B layer uses tool
Having dystectic polylactic acid blend, compared with inorganic nucleator, this nucleator and Poly-L-lactic acid have the preferable compatibility,
Sheet material can be made to have preferable toughness, it is not necessary to additional compatilizer, reduce precipitate.Use star polylactic acid as melt strength
Reinforcing agent, reduce firstly the difference of flowability of A, B interlayer, makes different interfacial bonding strength more preferable, it is easier to molding, next is adopted
Can be preferable with each layer main material compatibility as melt reinforcing agent with the polylactic acid of special construction.The preparation side that the present invention provides
Method is biaxial stretch-formed for not existing, and is not result in fabrication warpage.Therefore, PLA sheet material prepared by the present invention has heat-resist, can be around
The advantages such as line, fabrication not warpage, can substitute PVC and make for smart card.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Below describe in excellent
Select embodiment to be only used as citing, it may occur to persons skilled in the art that other obvious modification.
The present invention provides a kind of PLA sheet material, for A/B/A structure, is prepared by three-layer co-extruded technique, and A layer is by following component
Preparation: PLA resin 86-92 weight portion, melt strength enhancers 7-12 weight portion, light stabilizer 0.5-1 weight portion, antioxidant
0.5-1 weight portion.
Described PLA resin is poly-dl-lactide, for undefined structure, can quickly cool down, in ultrasound wave coiling after melting
Time can quickly metal wire be solidificated in sheet surface, currently preferred poly-dl-lactide mean molecule quantity is 140,000-16 ten thousand.
Described melt strength enhancers is the star polylactic acid with four paws structure, lactide cause at tetrahydroxy amylalcohol
Under, stannous octoate is the polylactic acid that catalyst prepares, and has the advantages that melt strength is big, can serve as melt strength enhancers,
Make melt curtain stable, and the linear chain structure of the strand of star structure and polylactic acid is mutually wound around, and can improve the strong of sheet material
Degree, currently preferred melt strength enhancers mean molecule quantity is 200,000-24 ten thousand.
Described light stabilizer is the one in UV531, UV770, can neutralize what polylactic acid produced under action of ultraviolet light
Free radical, stops the light degradation of polylactic acid, and the light stabilizer of the present invention is more preferably UV770.
Described antioxidant is at least one in I1010, I1076, can slow down polylactic acid in molding process
Oxidative degradation, and it is not result in that sheet surface produces frosting phenomenon.
B layer is prepared by following component: PLA resin 83-88.5 weight portion, melt strength enhancers 9-12 weight portion, nucleation
Agent 2-4 weight portion, antioxidant 0.5-1 weight portion.
Described PLA resin is Poly-L-lactic acid, has crystallinity, owing to smart card needs certain light-proofness, therefore adds
Adding and account for the Rutile type titanium dioxide that gross weight 10% particle diameter is 50-80 nanometer, the preferred mean molecule quantity of the present invention is 170,000-19
Ten thousand.
Described nucleator is a kind of Poly-L-lactic acid and dextrorotation polylactic acid blend, complementary mutually in two kinds of polylactic acid structures
Filling, compound with regular structure is tight, and the blend fusing point relatively Poly-L-lactic acid of formation is high, in molding process, works as Poly-L-lactic acid
During in viscous state, this nucleator is elastomeric state, and make can induce Poly-L-lactic acid crystallization, the one-tenth of the present invention in cooling procedure
It is Poly-L-lactic acid that core agent preferably forms mass ratio: dextrorotation polylactic acid is equal to 55%:45%, fusing point 245 DEG C, mean molecule
Amount is 200,000-22 ten thousand.
Melt strength enhancers is the star polylactic acid with four paws structure, by lactide under tetrahydroxy amylalcohol causes,
Stannous octoate is the polylactic acid that catalyst prepares, and has the advantages that melt strength is big, can serve as melt strength enhancers, makes to melt
Body curtain is stable, and the polylactic acid of the strand of star structure and linear chain structure is mutually wound around, and can improve the intensity of sheet material,
Inventing preferred melt strength enhancers mean molecule quantity is 260,000-28 ten thousand.
Described antioxidant is at least one in I1010, I1076, can slow down polylactic acid in molding process
Oxidative degradation, and it is not result in that sheet surface produces frosting phenomenon.
Accordingly, the present invention also provides for a kind of PLA preparation method, comprises the following steps:
(1) by A layer, B layer by respective proportioning mix homogeneously, it is separately added into corresponding feed bin.
(2) material plastifies through respective extruder, filter filters, Melt Pump is measured, melt distribution, by multiple in mould
Close, three-roller calendar cools down, rolling, prepares the PLA sheet material with A/B/A structure.
Described extruder temperature is A layer: 155 DEG C-190 DEG C, and rotating speed is 20-40r/min;B layer: 160 DEG C-200 DEG C, turns
Speed is 20-60r/min.
Described filter temperature is A layer: 185 DEG C-190 DEG C;B layer: 190 DEG C-195 DEG C.
Described Melt Pump temperature is 185 DEG C-195 DEG C;B layer: 190 DEG C-195 DEG C.
Described mould is co-extrusion monolayer mold, realizes the compound of A, B layer in mould, and different interfacial bonding strengths are big, temperature
Degree is 195 DEG C-200 DEG C.
Described three-roller calendar temperature is 40-45 DEG C of upper roller, central roll 25-30 DEG C, lower roll 25-30 DEG C, makes sheet material the coldest
But.
Described A layer thickness is 20-40 micron, it is provided that adequate thickness space solidification coil, it is micro-that the present invention is preferably 25
-35 microns of rice.
In order to be further appreciated by the present invention, the technical scheme provided the present invention below in conjunction with embodiment is carried out specifically
Bright, protection scope of the present invention is not limited by the following examples.
Various PLA resin used in the following embodiment of the present invention are provided by natureworks company.
Light stabilizer used in the following embodiment of the present invention is from Germany's BASF.
Antioxidant used in the following embodiment of the present invention comes from Ciba of Switzerland.
For the ease of comparing, the PLA sheet thickness that all embodiments prepare is 300 microns, and A layer thickness is 30 microns.
Embodiment 1
Various raw material is weighed according to hereinafter described mass fraction ratio
A layer: PLA resin 86 weight portion, melt strength enhancers 12 weight portion, light stabilizer UV770 1 weight portion, antioxygen
Agent I1076 1 weight portion.
B layer: PLA resin 83 weight portion, melt strength enhancers 12 weight portion, nucleator 4 weight portion, antioxidant I10761
Weight portion.
A kind of PLA sheet manufacturing process is as follows:
(1) A layer, each component raw material of B layer being separately added into high mixer mix homogeneously, add extruder plasticizing, A layer is corresponding
Parameter be extruder 155 DEG C-185 DEG C, rotating speed be 20r/min, filter 185 DEG C, Melt Pump 185 DEG C;B layer is right
Answering parameter is extruder 165 DEG C-200 DEG C, and rotating speed is 20r/min, filter 195 DEG C, Melt Pump 195 DEG C, mould
It it is 195 DEG C.
(2) melt obtains PLA sheet material through calender cooling, rolling, and wherein calender chilling temperature is 40 DEG C of upper roller, central roll
25 DEG C, lower roll 25 DEG C.
Embodiment 2
Various raw material is weighed according to hereinafter described mass fraction ratio
A layer: PLA resin 86 weight portion, melt strength enhancers 12 weight portion, light stabilizer UV770 1 weight portion, antioxygen
Agent I1076 1 weight portion.
B layer: PLA resin 88.5 weight portion, melt strength enhancers 9 weight portion, nucleator 2 weight portion, antioxidant I1076
0.5 weight portion.
A kind of PLA sheet manufacturing process is as follows:
(1) A layer, each component raw material of B layer being separately added into high mixer mix homogeneously, add extruder plasticizing, A layer correspondence is joined
Number is 40r/min for extruder 160 DEG C-190 DEG C, rotating speed, filter 190 DEG C, Melt Pump 195 DEG C;B layer correspondence parameter is extrusion
160 DEG C-195 DEG C of machine, rotating speed is 60r/min, filter 190 DEG C, Melt Pump 190 DEG C, and mould is 200 DEG C.
(2) melt obtains PLA sheet material through calender cooling, rolling, and wherein calender chilling temperature is 45 DEG C of upper roller, central roll
30 DEG C, lower roll 30 DEG C.
Embodiment 3
Various raw material is weighed according to hereinafter described mass fraction ratio
A layer: PLA resin 92 weight portion, melt strength enhancers 7 weight portion, light stabilizer UV770 0.5 weight portion, anti-
Oxygen agent I1076 0.5 weight portion.
B layer: PLA resin 83 weight portion, melt strength enhancers 12 weight portion, nucleator 4 weight portion, antioxidant I10761
Weight portion.
A kind of PLA sheet manufacturing process is as follows:
(1) A layer, each component raw material of B layer being separately added into high mixer mix homogeneously, add extruder plasticizing, A layer correspondence is joined
Number is 30r/min for extruder 160 DEG C-185 DEG C, rotating speed, filter 188 DEG C, Melt Pump 190 DEG C;B layer correspondence parameter is extrusion
165 DEG C-190 DEG C of machine, rotating speed is 40r/min, filter 192 DEG C, Melt Pump 193 DEG C, and mould is 197 DEG C.
(2) melt obtains PLA sheet material through calender cooling, rolling, and wherein calender chilling temperature is 43 DEG C of upper roller, central roll
28 DEG C, lower roll 28 DEG C.
Embodiment 4
Various raw material is weighed according to hereinafter described mass fraction ratio
A layer: PLA resin 92 weight portion, melt strength enhancers 7 weight portion, light stabilizer UV770 0.5 weight portion, anti-
Oxygen agent I1076 0.5 weight portion.
B layer: PLA resin 88.5 weight portion, melt strength enhancers 9 weight portion, nucleator 2 weight portion, antioxidant I1076
0.5 weight portion.
A kind of PLA sheet manufacturing process is performed by embodiment 3 preparation method.
Embodiment 5
Various raw material is weighed according to hereinafter described mass fraction ratio
A layer: PLA resin 90 weight portion, melt strength enhancers 8.5 weight portion, light stabilizer UV770 0.8 weight portion,
Antioxidant I1076 0.7 weight portion.
B layer: PLA resin 85 weight portion, melt strength enhancers 11.2 weight portion, nucleator 3 weight portion, antioxidant
I1076 0.8 weight portion.
A kind of PLA sheet manufacturing process is performed by embodiment 3 preparation method.
Comparative example 1
Implement according to the patent of invention disclosure that license notification number is " CN 103087483B ", prepare 300 microns
Biaxial stretch-formed PLA sheet material, as a comparison.
Comparative example 2
Test PVC smart card sheet properties, as a comparison.
Respectively the PLA sheet material of embodiment of the present invention 1-5 is detected, and contrast with comparative example, result such as table 1 institute
Show.
The PLA sheet material of table 1 embodiment of the present invention 1-5, comparative example 1 preparation and comparative example 2 the performance test results
The test result corresponding from embodiment 1-5 it can be seen that the present invention prepare PLA sheet material elongation at break, stretching
Intensity, vicat softening temperature are all low unlike comparative example 1, and coiling effect and full card angularity are superior to comparative example 1;With comparative example 2
Comparing, embodiment 1-5 performance is the most close, can be used for smart card and makes.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry
The personnel simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
Principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these change and
Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and
Equivalent defines.
Claims (10)
1. a PLA sheet material, for A/B/ A structure, it is characterised in that each component of A layer is: PLA resin 86-92 weight portion, molten
Body intensity reinforcing agent 7-12 weight portion, light stabilizer 0.5-1 weight portion, antioxidant 0.5-1 weight portion;The each component of B layer is: PLA
Resin 83-88.5 weight portion, melt strength enhancers 9-12 weight portion, nucleator 2-4 weight portion, antioxidant 0.5-1 weight
Part.
PLA sheet material the most according to claim 1, it is characterised in that in the described each component of A layer, PLA resin is that raceme gathers
Lactic acid, mean molecule quantity is 140,000-16 ten thousand;
Melt strength enhancers is the star polylactic acid with four paws structure, and mean molecule quantity is 20-24 ten thousand;
Light stabilizer is the one in UV531, UV770;
Antioxidant is at least one in I1010, I1076.
PLA sheet material the most according to claim 1, it is characterised in that in the described each component of B layer, PLA resin is left-handed poly-breast
Acid, containing accounting for the Rutile type titanium dioxide that gross weight 10% particle diameter is 50-80 nanometer, mean molecule quantity is 170,000-19 ten thousand;
Nucleator is a kind of Poly-L-lactic acid and dextrorotation polylactic acid blend, and composition mass ratio is Poly-L-lactic acid: the poly-breast of dextrorotation
Acid is equal to 55%:45%, and fusing point 245 DEG C, mean molecule quantity is 200,000-22 ten thousand;
Melt strength enhancers is the star polylactic acid with four paws structure, and mean molecule quantity is 26-28 ten thousand;
Antioxidant is at least one in I1010, I1076.
4. the preparation method of a PLA sheet material, it is characterised in that comprise the following steps:
(1) by A layer, B layer by respective proportioning mix homogeneously, it is separately added into corresponding feed bin;
(2) material plastifies through respective extruder, filter filters, Melt Pump is measured, melt distribution, by being combined in mould,
Three-roll press-polishing cooling press polish, rolling, prepare the PLA sheet material with A/B/A structure.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described extruder temperature is A
Layer: 155 DEG C-190 DEG C, rotating speed is 20-40r/min;B layer: 160 DEG C-200 DEG C, rotating speed is 20-60r/min.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described filter temperature is A
Layer: 185 DEG C-190 DEG C;B layer: 190 DEG C-195 DEG C.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described Melt Pump temperature is 185
℃-195℃;B layer: 190 DEG C-195 DEG C.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described mould is co-extrusion monolayer
Mould, temperature is 195 DEG C-200 DEG C.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described three-roller calendar temperature
For 40-45 DEG C of upper roller, central roll 25-30 DEG C, lower roll 25-30 DEG C.
The preparation method of a kind of PLA sheet material the most according to claim 4, it is characterised in that described prepared PLA sheet material A
Layer thickness 20 microns-40 microns.
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CN112708250A (en) * | 2020-12-23 | 2021-04-27 | 湖南工业大学 | High-permeability high-barrier polylactic acid material and preparation method and application thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109099223A (en) * | 2018-05-31 | 2018-12-28 | 安徽玉发塑业有限公司 | A kind of PVC drain pipe of high bearing capacity |
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CN112708250A (en) * | 2020-12-23 | 2021-04-27 | 湖南工业大学 | High-permeability high-barrier polylactic acid material and preparation method and application thereof |
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