CN105440621B - PLA noctilucence master batch and preparation method thereof - Google Patents
PLA noctilucence master batch and preparation method thereof Download PDFInfo
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- CN105440621B CN105440621B CN201610029921.XA CN201610029921A CN105440621B CN 105440621 B CN105440621 B CN 105440621B CN 201610029921 A CN201610029921 A CN 201610029921A CN 105440621 B CN105440621 B CN 105440621B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004626 polylactic acid Substances 0.000 claims abstract description 54
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 18
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000005299 abrasion Methods 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000000630 rising effect Effects 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- 239000013538 functional additive Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004017 vitrification Methods 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
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of a high polymer material, in particular to a PLA noctilucence master batch and a preparation method thereof. The PLA noctilucence master batch is prepared from following components in percent by mass: 50-60% of polylactic acid, 5-10% of auxiliaries, 30-40% of noctilucence powder, wherein the auxiliaries are polyethylene wax and/or zinc stearate; the weight-average molecular weight of the polylactic acid is 50,000-100,000. Compared with the prior art, by improving process conditions of extrusion through a single screw rod, reduction of an extruding rate, rising of a machining temperature, low speed mixing of a plastic cylinder and the like, abrasion to the machine caused by the noctilucence powder in a production process is reduced, and a blackening phenomenon of the noctilucence powder is avoided; the machining temperature is increased, so a cladding property of a melt for the noctilucence powder is improved, and the PLA noctilucence master batch with high noctilucence powder concentration can be produced; the PLA noctilucence master batch has the advantages of durable light emitting, large molecular weight of the PLA, small abrasion to the machine, uniform dispersion, wide applicable range and the like.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of PLA noctilucence master batch and preparation method thereof.
Background technology
Polylactic acid (PLA) is a kind of new biodegradation material, and its mechanical performance and physical property is good, possesses good
Glossiness well and transparency, while with good tensile strength and extensibility.PLA adds suitable for blowing, thermoplastic etc. are various
Work method, easy to process, using quite varied, the compatibility is good with degradability.In recent years, sending out with functional agglomerate technology
Exhibition, noctilucence master batch develops also quickly.But existing noctilucence master batch causes using limited due to there are many defects.Due to night
The hardness is bigger of light powder particles, fusing point are high, during melting mixing luminescent powder to rubbing inside screw rod and machine, easily
There are iron filings, cause metallic pollution, make master batch turning black and changing color, it is larger to the degree of wear of screw rod.Simultaneously noctilucence master batch is being used
In have certain requirement to matrix color, saturate matrix resin generates covering, makes night to the illumination effect of noctilucence master batch
The luminosity of light product is little, and fluorescent lifetime is short, and current matrix resin typically has polyethylene, polypropylene, polystyrene etc..
The concentration of noctilucence composition is relatively low in PLA noctilucence master batches, normally only between 10%-30%.The vitrification point of PLA is about 60
DEG C, it is glassy state under amorphous fraction room temperature, degraded is easily produced, therefore the relatively low PLA noctilucence master batches of molecular weight can only be produced.
The content of the invention
The present invention to solve prior art in noctilucence master batch in process of production turning black and changing color, fluorescent lifetime be short, luminescent powder
A kind of low problem of content, there is provided PLA noctilucence master batch and preparation method thereof, the noctilucence master batch long-acting illuminating, to wear and tear in machines
It is little, applied widely.
What the present invention was realized in：A kind of PLA noctilucence master batch, by weight percent proportioning is its component：
Polylactic acid 50%-65%
Auxiliary agent 5%-10%
Luminescent powder 30%-40%
The auxiliary agent is Tissuemat E and/or zinc stearate；
The weight average molecular weight of the polylactic acid is 50000-100000.
Instant invention overcomes the technology prejudice of this area, using the high PLA of molecular weight as matrix resin and high-load
Luminescent powder prepares noctilucence master batch.Its noctilucence powder content of the noctilucence master batch of preparation is not high in prior art, is limited by production technology
System, due to containing more metallic in luminescent powder, metallic hardness is bigger, heat absorption coefficient is larger, when noctilucence powder content
During increase, metallic increases with the friction probability of machine inwall, causes blackening phenomena serious.Meanwhile, the PLA of higher molecular weight
In preparing noctilucence master batch, process relatively difficult, such as processing temperature is too high can cause melt flow rate (MFR) too fast.
The present invention is blended using high molecular PLA with 30-40wt% luminescent powders, in mixing process, as luminescent powder contains
The increase of amount, its heat absorption coefficient is larger, and at a temperature of same production, the timing of mixing time one, the actual temperature of melt has one
Fixed rising, the processing to high molecular PLA provides facility, and the production temperature of such as master batch is 150-170 DEG C, in practice
When PLA processing temperature can be more than 190 DEG C.Inventor find when polylactic acid weight average molecular weight be 50000-100000 when,
Optimal noctilucence master batch is obtained.The polylactic acid, fusing point is 175 DEG C -185 DEG C, and density is 1.20-1.30kg/L, and feature is glued
Number IV is 0.2-8dl/g.
The auxiliary agent can be the mixture of Tissuemat E, zinc stearate or Tissuemat E and zinc stearate, when to gather
When ethylene waxes and zinc stearate mixture, Tissuemat E is 4 with the mass ratio of zinc stearate：1.
To reach more preferable effect, the fusing point of Tissuemat E of the present invention is 100-106 DEG C, and molecular weight is 3000-
5000。
Further, the luminescent powder is luminescent powder Y-8D.The granular size of luminescent powder directly affects noctilucence powder particles
Dispersibility in matrix resin, granule is less, and dispersibility is better and can reduce friction, when luminescent powder mesh number be 800 mesh with
When upper, its performance is optimal.
To reach some specific functions, the present invention can also improve other property of master batch by adding functional additive
Energy, such as antistatic additive, fire retardant, brightener, antibacterial, antioxidant.
The present invention is claimed the preparation method of above-mentioned PLA noctilucence master batch simultaneously.
The method is comprised the following steps：Each component is weighed by weight ratio and low speed batch mixing in barrel is added to, and mixing is equal
After even, rotating speed is added in 80～250r/min extruders, to extrude after melting mixing at a temperature of 170-230 DEG C and making
Grain, is then dried, and packs, and obtains final product PLA noctilucence master batches.
Any one barrel for containing raw material that the barrel can be known in the art, such as plastics barrel, are reduction
The phenomenon that noctilucence granule causes to wear and tear and then make luminescent powder blackening to machine in production process, using barrel low speed batch mixing, Jing sends out
The substantial amounts of technique of a person of good sense is groped, and the rotating speed of low speed batch mixing is 60r/min.
On expressing technique, the present invention does not select this area to widely use double screw extruder or multi-screw extruder
Extruded, but extruded with relatively low 80～250r/min of rotating speed from single screw extrusion machine, because Single screw extrusion and low
Rate of extrusion can reduce shearing force in extrusion, the metal that luminescent powder can be avoided to produce during melting mixing
Pollution.To reach more preferable effect, extruder rotating speed is 100～200r/min.
Compared with prior art, the invention has the beneficial effects as follows：Added by Single screw extrusion, reduction rate of extrusion, rising
The improvement of the process conditions such as work temperature and plastics barrel low speed batch mixing, reduces abrasion of the luminescent powder to machine in production process,
Avoid producing luminescent powder blackening phenomena；Processing temperature is raised, cladding ability of the melt to luminescent powder is improved, luminescent powder concentration is produced
High PLA noctilucence master batches；PLA noctilucence master batch of the present invention have noctilucence phase concentration height, long-acting illuminating, PLA molecular weight it is big, to machine
Abrasion is little, the advantages of be uniformly dispersed and be applied widely.
Specific embodiment
Technical scheme is further illustrated with reference to specific embodiment, following embodiments are not used in restriction originally
The protection domain of invention, if no special instructions, chemicals involved in the present invention or raw material chemically company can be obtained.It is described
The preferred luminescent powder Y-8D of luminescent powder is purchased from Zhongbang, Chemical Industry Co., Ltd., Dalian.
Embodiment 1
A kind of PLA noctilucence master batch, by weight percent proportioning is its component：
Polylactic acid 50%, Tissuemat E 6%, zinc stearate 1.5%, luminescent powder 40%, functional additive surplus.Its system
Preparation Method is as follows：
Each component is weighed by weight ratio, first polylactic acid and luminescent powder are added in plastics barrel, be subsequently adding poly- second
Mixture (the mass ratio 4 of alkene wax and zinc stearate:1), functional additive, in rotating speed 60r/min low speed batch mixers 3 are mixed
Minute, it is to be mixed it is uniform after, screw speed is added to in 100r/min single screw extrusion machines, at a temperature of 170 DEG C -230 DEG C
The extruding pelletization after melting mixing, is then dried, packaging, obtains final product PLA noctilucence master batches.
Embodiment 2
A kind of PLA noctilucence master batch, by weight percent proportioning is its component：
Polylactic acid 65%, Tissuemat E 4%, zinc stearate 1%, luminescent powder 30%.
Its preparation method is as follows：
Each component is weighed by weight ratio, and first polylactic acid and luminescent powder are added in plastics barrel, then in proportion 4：1
The mixture of Tissuemat E and zinc stearate is added, is mixed 3 minutes in rotating speed 60r/min low speed batch mixers, it is to be mixed uniform
Afterwards, screw speed is added in 150r/min single screw extrusion machines, to extrude after melting mixing at a temperature of 200 DEG C and making
Grain, is then dried, and packs, and obtains final product PLA noctilucence master batches.
Embodiment 3
A kind of PLA noctilucence master batch, by weight percent proportioning is its component：
Polylactic acid 55%, Tissuemat E 8%, zinc stearate 2%, luminescent powder 35%.
Its preparation method is as follows：
Each component is weighed by weight ratio, and first polylactic acid and luminescent powder are added in plastics barrel, then in proportion 4：1
The mixture of Tissuemat E and zinc stearate is added, is mixed 3 minutes in rotating speed 60r/min low speed batch mixers, it is to be mixed uniform
Afterwards, screw speed is added in 120r/min single screw extrusion machines, to extrude after melting mixing at a temperature of 170 DEG C DEG C and making
Grain, is then dried, and packs, and obtains final product PLA noctilucence master batches.
Embodiment 4
A kind of PLA noctilucence master batch, by weight percent proportioning is its component：
Polylactic acid 55%, Tissuemat E 6%, zinc stearate 1.5%, luminescent powder 35%, functional additive surplus.Its system
Preparation Method is as follows：
Each component is weighed by weight ratio, first polylactic acid and luminescent powder are added in plastics barrel, be subsequently adding poly- second
Mixture (the mass ratio 4 of alkene wax and zinc stearate:1), functional additive, in rotating speed 60r/min low speed batch mixers 3 are mixed
Minute, it is to be mixed it is uniform after, screw speed is added to in 120r/min single screw extrusion machines, through molten at a temperature of 230 DEG C
Melt extruding pelletization after mixing, be then dried, pack, obtain final product PLA noctilucence master batches.
The PLA noctilucence master batch performance test of the present invention of table 1
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of PLA noctilucence master batch, it is characterised in that comprise the following steps：Weigh each component and be added to material
Low speed batch mixing in cylinder, the rotating speed of low speed batch mixing is 60r/min, after mix homogeneously, is added to rotating speed for 100～200r/min extrusions
In machine, at a temperature of 170-230 DEG C after melting mixing extruding pelletization, be then dried, pack, obtain final product PLA noctilucence female
Grain；
By weight percent proportioning is each component：
Polylactic acid 50%-65%
Auxiliary agent 5%-10%
Luminescent powder 30%-40%
The auxiliary agent is Tissuemat E and/or zinc stearate；
The weight average molecular weight of the polylactic acid is 50000-100000；
The luminescent powder is luminescent powder Y-8D.
2. the preparation method of PLA noctilucence master batch according to claim 1, it is characterised in that the auxiliary agent is Tissuemat E
During with zinc stearate, Tissuemat E is 4 with the mass ratio of zinc stearate：1.
3. the preparation method of PLA noctilucence master batch according to claim 1, it is characterised in that the fusing point of the Tissuemat E
For 100-106 DEG C, molecular weight is 3000-5000.
4. the preparation method of PLA noctilucence master batch according to claim 1, it is characterised in that the extruder is single screw rod
Extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610029921.XA CN105440621B (en) | 2016-01-15 | 2016-01-15 | PLA noctilucence master batch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610029921.XA CN105440621B (en) | 2016-01-15 | 2016-01-15 | PLA noctilucence master batch and preparation method thereof |
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| Publication Number | Publication Date |
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| CN105440621A CN105440621A (en) | 2016-03-30 |
| CN105440621B true CN105440621B (en) | 2017-05-03 |
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| CN110724384A (en) * | 2019-11-06 | 2020-01-24 | 佛山市钜亮光学材料有限公司 | Multipurpose noctilucent powder particle and preparation method thereof |
| CN111269540A (en) * | 2020-03-22 | 2020-06-12 | 宿迁联盛科技股份有限公司 | Special high-concentration flame-retardant master batch for polylactic acid and preparation method thereof |
| CN114634637B (en) * | 2022-03-02 | 2024-01-30 | 江苏普莱克红梅色母料股份有限公司 | Luminous masterbatch for polypropylene non-woven fabrics and its preparation method and application |
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| JP4635528B2 (en) * | 2003-09-12 | 2011-02-23 | 住友化学株式会社 | Luminescent material and light emitting device using the same |
| RU2470791C2 (en) * | 2008-01-25 | 2012-12-27 | Дзе Проктер Энд Гэмбл Компани | Thermoplastic material containing polychromic substances |
| CN104530597B (en) * | 2014-12-24 | 2017-02-08 | 浙江理工大学 | Biodegradable pearlescent pen shell and preparation method thereof |
| CN105802162A (en) * | 2015-05-29 | 2016-07-27 | 江苏浩宇电子科技有限公司 | Application of 3D printing material with mosquito repellent and luminous effects |
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