CN106189129A - A kind of PLA sheet material and preparation method thereof - Google Patents

A kind of PLA sheet material and preparation method thereof Download PDF

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Publication number
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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layer
sheet material
pla
weight portion
preparation
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CN106189129B (en
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李英
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Weihai polyyan New Material Co., Ltd.
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李英
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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
    • B29C48/16—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

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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)
  • 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

A kind of PLA sheet material and preparation method thereof
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.
CN201610534912.6A 2016-07-07 2016-07-07 A kind of PLA sheet materials and preparation method thereof Active CN106189129B (en)

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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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