CN106751615A - A kind of high dispersive, biodegradable Masterbatch of low water absorption and preparation method thereof - Google Patents
A kind of high dispersive, biodegradable Masterbatch of low water absorption and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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Abstract
The present invention relates to a kind of high dispersive, the biodegradable Masterbatch of low water absorption and preparation method thereof, it is composed of the following components that the biodegradable Masterbatch presses mass fraction：18~90 parts of noncrystalline PLA, 2~20 parts of biodegradable plasticizer, 0.5~80 part of pigment, 0~72.5 part of filler；Wherein, the biodegradable plasticizer is acetyl epoxidized fatty acid ester.The biodegradable Masterbatch that the present invention is provided is with noncrystalline PLA as carrier; with specific acetyl epoxidized fatty acid ester as plasticizer and dispersant; the Masterbatch good dispersion for preparing, water absorption rate are low, wide adaptation range; the coloring of PLA is applicable not only to, preferable coloring effect is respectively provided with to polycaprolactone (PCL), poly-succinic fourth diester (PBS), poly terephthalic acid adipic acid fourth diester (PBAT) etc..Nondegradable carrier or dispersant are free of in the formula of the Masterbatch that the present invention is provided, with fully biodegradable characteristic.
Description
Technical field
The invention belongs to field of plastic coloring, and in particular to a kind of high dispersive, the biodegradable Masterbatch of low water absorption
And preparation method thereof.
Background technology
Biodegradable material refers to that a class passes through compost treatment in nature, (true in microorganism such as bacterium, mould
Bacterium) and Algal Effects under cause the material of degraded.Preferable biodegradation material be a kind of performance it is excellent, it is discarded after can quilt
Environmental microorganism decomposes, ultimately forms a macromolecular material for part of Carbon cycle in nature completely.
As the enhancing of environmental consciousness and countries in the world legislation are put into effect in succession, biodegradable new material industry faces new hair
Exhibition opportunity.The developed countries and regions such as Europe, the United States, day are worked out and have put into effect relevant regulation in succession, by local disabling, are limited the use of, by force
The use that the measures such as pollution tax limit non-degradable plastics is collected and collected to system, greatly develops biodegradable new material, to protect
Retaining ring border, soil protection, wherein France's i.e. appearance all disposable plastic bags of carrying of Policy Conditions in 2005 must after 2010
Must be biodegradable.China has also put into effect the application and popularization that multinomial policy encourages biodegradable plastic successively.The whole nation in 2004
The National People's Congress passes through《Renewable Energy Law (draft)》With《Solid waste method (revision)》, encourage regeneration biological mass-energy to utilize and degradative plastics
Popularization and application.
At present, Biodegradable material mainly has PLA (PLA), poly butylene succinate (PBS), adipic acid-right
The ester copolymer of phthalic acid-fourth two (PBAT), polycaprolactone (PCL), PHA (PHA), polyvinyl alcohol (PVA) and
Poly-beta-hydroxy-butyrate (PHB) etc..Wherein, PLA has good mechanical property, relative low price, is maximum current consumption
One of kind.
With biodegradation material high speed development and extensive use, to biodegradable Masterbatch the need for will increasingly increase
Plus.Chinese patent CN1368516, CN101392078, CN101319068 etc. use polyethylene or ethylene-vinyl acetate copolymer
It is carrier etc. non-degradable material, this necessarily affects the final degradation property of product.Chinese patent CN101475695 and
Although it is carrier that CN102040814 uses biodegradable plastic, but Tissuemat E, oxidation is also with the addition of in these patents and is gathered
The non-degradable auxiliary agent such as ethylene waxes or EBS, the Masterbatch for preparing cannot be degradable.In Chinese patent CN104151800
Silane coupler and titanate coupling agent are added with, cannot also be realized degradable.Selected in Chinese patent CN102391626
Although vector resin be bio-based can degradable polymer, any processing aid is not added with the patent, this causes color
Master batch in process of production pigment dispersion effect it is undesirable, processing viscosity it is larger, it is follow-up using easily there is color dot the problems such as.
It is contemplated that overcoming the shortcomings of that above-mentioned Masterbatch is present, there is provided a kind of totally biodegradable, dispersive property are excellent
The low Masterbatch of different, water absorption rate.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of high dispersive, the biology of low water absorption can drop
Solution Masterbatch, the present invention provide biodegradable Masterbatch with noncrystalline PLA as carrier, with specific acetyl epoxidation
Fatty acid ester is plasticizer and dispersant, and the Masterbatch totally biodegradable for preparing, good dispersion, water absorption rate are low, suitable
Answer scope wide, with preferable coloring effect.
Preparation side another object of the present invention is to provide above-mentioned high dispersive, the biodegradable Masterbatch of low water absorption
Method.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
18~90 parts of noncrystalline PLA, 2~20 parts of biodegradable plasticizer, 0.5~80 part of pigment, filler 0~
72.5 parts；Wherein, the biodegradable plasticizer is acetyl epoxidized fatty acid ester, the acetyl epoxidized fatty acid ester
Structure is as follows：
Wherein, m+n=14, m=5~9, n=5~9.
Acetyl epoxidized fatty acid ester is a kind of plasticizer from vegetable oil acid, itself has the good biology can
Degradation property.Present inventors have unexpectedly found that the effect with good dispersion, plasticising when using it for PLA primary colours master batches, can be notable
The dispersive property of pigment is improved, reducing the viscosity and water absorption rate of Masterbatch, the good dispersion effect of acquisition.In addition, and citric acid
Esters, Polymer polyester plasticizer are compared, and acetyl epoxidized fatty acid ester has that cheap and PLA compatibility is good, makes
The problems such as migration will not being produced with process.
Preferably, to press mass fraction composed of the following components for the biodegradable Masterbatch：
25~80 parts of noncrystalline PLA, 3~15 parts of biodegradable plasticizer, 1~70 part of pigment, filler 1~70
Part；Wherein, biodegradable plasticizer is stated for acetyl epoxidized fatty acid ester.
It is further preferable that the biodegradable Masterbatch to press mass fraction composed of the following components：
40 parts of noncrystalline PLA, 5 parts of biodegradable plasticizer, 40 parts of pigment, 15 parts of filler；Wherein, the life
Biodegradable plasticizer is acetyl epoxidized fatty acid ester；Wherein, the biodegradable plasticizer is acetyl epoxidized fat
Acid esters.
, with amorphism PLA as carrier, its softening transform temperature is more relatively low than crystalline polylactic acid, is with it for the present invention
The Masterbatch that raw material is prepared dispersive property in use is more preferable.In the present invention, the number of noncrystalline PLA is equal
Preparation influence of the molecular weight on Masterbatch is larger, and number-average molecular weight is excessive to cause material viscosity larger, and number-average molecular weight is too small
Material viscosity is smaller, and this can all have influence on the preparation of Masterbatch.Preferably, the number-average molecular weight of the noncrystalline PLA is
5000~200000；It is further preferable that the number-average molecular weight of the noncrystalline PLA is 50000~100000.
Preferably, the acetyl epoxidized fatty acid ester is acetyl epoxidised vegetable olein, diacetyl epoxidation
One or more in vegetable oil acid glyceride, the glyceride of acetyl epoxidised vegetable oleic acid two.
Preferably, the acetyl epoxidized fatty acid ester is acetyl epoxidised vegetable olein.
Preferably, the pigment is one or more in inorganic pigment, organic pigment.
Filler can to a certain extent increase the dispersive property of Masterbatch and reduce production cost, filling out in the present invention
Filling agent can select the conventional filler in this area.Preferably, the filler is starch, calcium carbonate, talcum powder, titanium dioxide
One or more in silicon, mica or barium sulfate.
Preferably, the organic pigment is one or more in phthalein green grass or young crops pigment, AZOpigments, acridine pigments；The nothing
Machine pigment is one or more in titanium dioxide, carbon black or iron oxide red.
The invention also discloses above-mentioned high dispersive, the preparation method of the biodegradable Masterbatch of low water absorption, the side
Method is：Weigh raw material by formula, be then pre-mixed uniformly the raw material, in extruder or banbury melting mixing, squeeze
Go out granulation to obtain final product.
Preferably, the temperature of the melting mixing is 130~170 DEG C, and the temperature of extruding pelletization is 130~190 DEG C, extrusion
The rotating speed of machine is 100~400rpm.
Compared with prior art, the present invention has the advantages that：
The present invention provide biodegradable Masterbatch with noncrystalline PLA as carrier, with acetyl epoxidized fatty acid ester
It is plasticizer and dispersant, the Masterbatch good dispersion for preparing, water absorption rate are low, wide adaptation range, is applicable not only to poly- breast
The coloring of acid, to polycaprolactone (PCL), poly-succinic fourth diester (PBS), poly terephthalic acid adipic acid fourth diester (PBAT)
With preferable coloring effect.Nondegradable carrier or dispersant are free of in the formula of the Masterbatch that the present invention is provided, are had
Fully biodegradable characteristic.
Specific embodiment
The present invention is further explained with reference to specific embodiment, but specific embodiment is not to the present invention
It is limited in any way.PLA is purchased from Naturework companies, its product designation 4060D in following embodiment；Acetyl epoxy
Change fatty acid ester plasticizer and be purchased from Guangzhou Hairma Chemicals Ltd., its product designation HM-828；Other pigment,
Filler etc. is material commonly used in the art.
In following embodiment, the percentage composition is weight percentage.
Embodiment 1
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4060D 18%, diacetyl epoxidised vegetable olein 2%, titanium dioxide 80%.
Said components are uniform using mixer premix, and it is 28 then to use draw ratio:1 single screw extrusion machine extrusion is made
Grain, extruder temperature is set as 60 DEG C, 130 DEG C, 130 DEG C, 130 DEG C, engine speed 100rpm.
Embodiment 2
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA4060D 30%, acetyl epoxidized fatty acid ester HM-828 20%, carbon black 40%, talcum powder 10%.
Said components are uniform using mixer premix, and then banbury carries out melting mixing, melting temperature 140 DEG C, turn
Fast 30rpm, it is 40 then to use draw ratio:1 double screw extruder extruding pelletization, extruder temperature be set as 60 DEG C, 150
DEG C, 150 DEG C, 150 DEG C, engine speed 300rpm.
Embodiment 3
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4060D 50%, single acetyl epoxidised vegetable olein 10%, titanium dioxide 10%, phthalocyanine blue 15%,
Calcium carbonate 10%, silica 5%.
Said components are uniform using mixer premix, and it is 48 then to use draw ratio:1 double screw extruder extrusion is made
Grain, extruder temperature is set as 60 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, engine speed 400rpm.
Embodiment 4
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4060D 40%, the glyceride 15% of acetyl epoxidised vegetable oleic acid two, sun-proof bright red 20%, acridine red 5%,
Barium sulfate 20%.
Said components are uniform using mixer premix, and it is 56 then to use draw ratio:1 double screw extruder extrusion is made
Grain, extruder temperature is set as 60 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, engine speed 400rpm.
Embodiment 5
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4060D 40%, acetyl epoxidized vegetable oil acid glyceride 10%, carbon black 0.2%, titanium dioxide 40%, phthalocyanine blue
1%th, mica 8.8%.
Said components are uniform using mixer premix, and it is 40 then to use draw ratio:1 double screw extruder extrusion is made
Grain, extruder temperature is set as 60 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, engine speed 300rpm.
Embodiment 6
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4060D 70%, diacetyl epoxidised vegetable olein 8%, dark green 2%, starch 20%.
Said components are uniform using mixer premix, and it is 40 then to use draw ratio:1 double screw extruder extrusion is made
Grain, extruder temperature is set as 60 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, engine speed 250rpm.
Comparative example 1
Any plasticizer is not added with the Masterbatch that this reference examples is provided, other components and content are same as Example 2, this
The Masterbatch that reference examples are provided is made up of by mass fraction following raw material：
PLA 4060D 30%, carbon black 40%, talcum powder 30%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
Comparative example 2
The acetyl ring that plasticizer in the Masterbatch that this reference examples is provided is come in alternate embodiment 2 from OPE
Oxidation of fat acid esters HM-828, other components and content are same as Example 2, and the Masterbatch that this reference examples is provided presses mass fraction
It is made up of following raw material：
PLA 4060D 30%, OPE 20%, carbon black 40%, talcum powder 10%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
Comparative example 3
The noncrystalline PLA come in alternate embodiment 2 from crystalline state PLA in the Masterbatch that this reference examples is provided,
Other components and content are same as Example 2, and the Masterbatch that this reference examples is provided is made up of by mass fraction following raw material：
A kind of biodegradable Masterbatch of high dispersive, low water absorption, the biodegradable Masterbatch presses mass fraction
It is composed of the following components：
PLA 4032D30%, acetyl epoxidized fatty acid ester HM-828 20%, carbon black 40%, talcum powder 10%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
Comparative example 4
This reference examples provide Masterbatch in acetyl epoxidized fatty acid ester HM-828 consumption it is less, other components and
Content is same as Example 2, and the Masterbatch that this reference examples is provided is made up of by mass fraction following raw material：
PLA4060D 97%, acetyl epoxidized fatty acid ester HM-828 1%, dark green 2%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
Comparative example 5
The consumption of the PLA in the Masterbatch that this reference examples is provided is less, and other components and content are same as Example 2, this
The Masterbatch that reference examples are provided is made up of by mass fraction following raw material：
PLA 4060D 15%, acetyl epoxidized fatty acid ester HM-828 10%, dark green 2%, talcum powder 73%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
Comparative example 6
Plasticizer in the Masterbatch that this reference examples is provided carrys out alternate embodiment 2 from tributyl 2-acetylcitrate (ATBC)
In acetyl epoxidized fatty acid ester HM-828, other components and content be same as Example 2, the Masterbatch that this reference examples is provided
It is made up of following raw material by mass fraction：
PLA4060D 30%, tributyl 2-acetylcitrate 20%, carbon black 40%, talcum powder 10%.
The preparation method of the Masterbatch that this reference examples is provided is with embodiment 2.
The moisture and biodegradable properties of the Masterbatch that embodiment 1~6 and comparative example 1~6 are prepared are surveyed
Examination, and obtained Masterbatch is respectively added in PLA and PBAT tests its dispersive property；Method of testing is as follows, test result
See the table below.
(1) moisture
The moisture of Masterbatch is carried out with reference to GB/T 6284-2006 methods, and specific method of testing is as follows：
Masterbatch is opened wide under field conditions (factors) and is placed 7 days, then accurately weigh 10g Masterbatch, contained using quick moisture
Amount instrument is tested 5 minutes at 120 DEG C.
(2) biodegradable properties
The biodegradable properties evaluation method of Masterbatch is：Masterbatch is pressed into the piece of 0.2mm thickness at 160 DEG C
Material, the disintegration of Masterbatch is tested according to the method in GB/T 19811-2005.
(3) dispersive property
The dispersive property of Masterbatch is tested according to the method in QB/1648-1992 5.7 sections, specific method of testing
It is as follows：
Prepared Masterbatch is added in 4% ratio carries out blown film through in abundant dry PLA, PBAT, observes
Whether occur striped in film and evaluate its uniform coloring, the number and size for counting color dot and fisheye evaluate its dispersive property.
The embodiment 1~6 of table 1 and comparative example 1~6 prepare the performance test of Masterbatch
Masterbatch blown film performance test in PLA prepared by the embodiment 1~6 of table 2 and comparative example 1~6
Remarks：There is plasticizer in comparative example.
Masterbatch blown film performance test in other Biodegradable materials prepared by 3 embodiment of table 3
From upper table 1, various embodiments of the present invention with the addition of Masterbatch moisture≤0.32% of HM-828 plasticizer,
Well below other each reference examples moistures (>=0.83%).Disintegration of the invention reaches more than 99%, hence it is evident that higher than adding
Plus the Masterbatch 79.3% of OPE.
Knowable to the experimental result of table 2, the biodegradable Masterbatch blown film good dispersion property prepared using the present invention,
Substantially do not occur striped in film, the color dot of diameter >=0.6mm does not have, diameter between color dot≤6 of 0.3~0.6mm/
m2；And contrast of fringes is more serious after Masterbatch prepared by each comparative example 1-5 is used for resin, color dot is more, although comparative example 6 disperse with
It is of the invention suitable, but because tributyl 2-acetylcitrate is not good with PLA compatibilities, Masterbatch surface finds there is plasticising after 2 days
The phenomenon that agent is separated out.
As known from Table 3, Masterbatch of the invention is in polycaprolactone (PCL), poly-succinic fourth diester (PBS), poly- to benzene two
Blown film tinctorial property is good in formic acid adipic acid fourth diester (PBAT).
It follows that the dispersive property of Masterbatch that the present invention is prepared is excellent, be applicable to PLA and PBAT
Color.The biodegradable Masterbatch that the present invention is provided has extensive in Biodegradable film, injection and fibre field
Application prospect.
Claims (10)
1. the biodegradable Masterbatch of a kind of high dispersive, low water absorption, it is characterised in that the biodegradable Masterbatch is pressed
Mass fraction is composed of the following components：
18~90 parts of noncrystalline PLA, 2~20 parts of biodegradable plasticizer, 0.5~80 part of pigment, filler 0~72.5
Part；Wherein, the biodegradable plasticizer is acetyl epoxidized fatty acid ester, the knot of the diacetyl epoxidized fatty acid ester
Structure is as follows：
Wherein, m+n=14, m=5~9, n=5~9.
2. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 1, it is characterised in that the biology
It is composed of the following components that Degradable masterbatch presses mass fraction：
25~80 parts of noncrystalline PLA, 3~15 parts of biodegradable plasticizer, 2~70 parts of pigment, 1~70 part of filler；Its
In, the biodegradable plasticizer is acetyl epoxidized fatty acid ester.
3. the biodegradable Masterbatch of high dispersive according to claim 1 or claim 2, low water absorption, it is characterised in that the second
Acyl epoxidized fatty acid ester is acetyl epoxidised vegetable olein, diacetyl epoxidised vegetable olein, acetyl ring
Oxidation the glyceride of vegetable oil acid two in one or more.
4. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 3, it is characterised in that the acetyl
Epoxidized fatty acid ester is acetyl epoxidised vegetable olein.
5. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 1, it is characterised in that the non-knot
The number-average molecular weight of brilliant PLA is 5000~200000.
6. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 5, it is characterised in that the non-knot
The number-average molecular weight of brilliant PLA is 50000~100000.
7. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 1, it is characterised in that the pigment
It is one or more in inorganic pigment, organic pigment；The filler is starch, calcium carbonate, talcum powder, silica, cloud
One or more in female or barium sulfate.
8. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 1, it is characterised in that described organic
Pigment is one or more in phthalein green grass or young crops pigment, AZOpigments, acridine pigments.
9. the biodegradable Masterbatch of high dispersive, low water absorption according to claim 1, it is characterised in that described inorganic
Pigment is one or more in titanium dioxide, carbon black or iron oxide red.
10. any high dispersive of claim 1~9, the preparation method of the biodegradable Masterbatch of low water absorption, its feature
It is that methods described is：Raw material is weighed by formula, is then pre-mixed uniformly the raw material, in extruder or banbury
Melting mixing, extruding pelletization are obtained final product.
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| CN113563703A (en) * | 2021-07-27 | 2021-10-29 | 南通市江能塑业有限公司 | Production process of degradable color master batch |
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