CN105440621B - PLA noctilucence master batch and preparation method thereof - Google Patents

PLA noctilucence master batch and preparation method thereof Download PDF

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Publication number
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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Prior art keywords
pla
noctilucence
master batch
preparation
noctilucence master
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CN105440621A (en
Inventor
刘元文
刘元政
刘云
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Dalian Crystal Color Masterbatch Co Ltd
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Dalian Crystal Color Masterbatch Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature

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

A kind of PLA noctilucence master batch and preparation method thereof
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.
CN201610029921.XA 2016-01-15 2016-01-15 PLA noctilucence master batch and preparation method thereof Active CN105440621B (en)

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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 master batch for polypropylene non-woven fabric and preparation method and application thereof

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DE112004001661T5 (en) * 2003-09-12 2006-07-06 Sumitomo Chemical Co., Ltd. A light emitting material and light emitting device using the same
BRPI0906583A2 (en) * 2008-01-25 2019-09-24 Procter & Gamble thermoplastic material comprising polychromic substances
CN104530597B (en) * 2014-12-24 2017-02-08 浙江理工大学 Biodegradable pearlescent pen shell and preparation method thereof
CN104861603B (en) * 2015-05-29 2016-08-17 江苏浩宇电子科技有限公司 A kind of 3D printed material with anophelifuge and luminous effect and application

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