CN110128805A - A kind of polylactic acid Masterbatch and preparation method thereof - Google Patents
A kind of polylactic acid Masterbatch and preparation method thereof Download PDFInfo
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- CN110128805A CN110128805A CN201910497285.7A CN201910497285A CN110128805A CN 110128805 A CN110128805 A CN 110128805A CN 201910497285 A CN201910497285 A CN 201910497285A CN 110128805 A CN110128805 A CN 110128805A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/463—Edible packaging materials
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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
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C08K5/00—Use of organic ingredients
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- C08K5/098—Metal salts of carboxylic acids
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- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
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Abstract
The present invention discloses a kind of polylactic acid Masterbatch and preparation method thereof, raw material components including following parts by weight: 100 parts of polylactic acid, DL- third hands over 10~20 parts of rouge, 0.3~0.6 part of food grade pigment, 0.3~0.6 part of lubrication dispersing agent, compound 0.2~0.6 part of nucleating agent, 0.3~0.6 part of chain extender, 6~9 parts of polyvinyl alcohol, 12~16 parts of reinforcing filler；The present invention hands over rouge as the carrier of carrying pigment using DL- third; polyvinyl alcohol protects auxiliary agent as the cladding of pigment; pass through the effect of chain extension initiator; realize that DL- third hands over the compound of rouge and polylactic acid carrier in twin-screw extrusion; realize the pigment dispersion of Nano grade; the chain carrier of rouge is handed over using initiator remaining in polylactic acid as DL- third in pigment preparations, is realized the combination of pigment preparations and polylactic acid molecule, is completed the strong dispersion effect of organic pigment.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of high dispersive polylactic acid Masterbatch and preparation method thereof.
Background technique
As environmental issue is paid attention in the raising and government of people's environmental consciousness further, cause Biodegradable material a large amount of
Applied to disposable product, such as non-returnable container material, disposable tableware etc..Simultaneously, these disposable biodegradable systems
The coloring of product also becomes essential a part.Because disposable tableware is directly and human contact, disposable tableware
Coloring must satisfy this two big important indicator of safety and sanitation.
The dispersion of pigment is the inevitable problem of Masterbatch industry, and traditional increase pigment is dispersed in Masterbatch
Method, usually realized by the effect of the mixed at high speed of high mixer and various lubrications, dispersion, increase-volume auxiliary agent, such as in face
EBS dispersing agent, stearic acid lubricant, maleic anhydride grafting, the increasing of glycidyl methacrylate class are added in material and carrier
Hold agent, the auxiliary agents such as diffusing oil, then by double screw extruder or three-screw extruder, mixing kneader device etc. completes Masterbatch
Preparation, although the above method can promote dispersion of the pigment in resin carrier, effect is poor, higher cost, is easy to draw
The disadvantages of entering lower-molecular substance.
Chinese patent CN201510507819.1 discloses a kind of bamboo powder and polylactic acid handled through lactide surface grafting
Blended compound material and the preparation method and application thereof is that bamboo powder is first carried out the processing of lactide surface grafting, i.e., in certain temperature and
Under mixing speed, the reaction under stannous octoate catalyst effect of bamboo powder and lactide mixture obtains the processing of lactide surface grafting
Bamboo powder.Then, by the bamboo powder handled through lactide surface grafting (can be 10~90 parts), polylactic acid (can be 10~90 parts)
Composite material is made with (2~5 parts) progress melt blendings of a small amount of heat stabilizer.The invention is in the mistake for carrying out grafting processing to bamboo powder
Toluene, chloroform, the poisonous and harmful solvent of stannous octoate and catalyst are used in journey, although these auxiliary agents are conducive to bamboo powder and hand over third
Rouge comes into full contact with and reacts, but there are this solvents to be difficult to recycle, and by-product is difficult to the problem of separating.
Chinese patent CN201611181001.6 disclose a kind of high dispersive, low water absorption biodegradable Masterbatch and
Preparation method, the biodegradable Masterbatch are composed of the following components by mass fraction: 18~90 parts of noncrystalline polylactic acid,
2~20 parts of biodegradable plasticizer, 0.5~80 part of pigment, 0~72.5 part of filler；Wherein, the biodegradable plasticising
Agent is acetyl epoxidized fatty acid ester.Only select acetyl epoxidized fatty acid ester as polylactic acid color masterbatch in the invention patent formulation
The plasticizer and dispersing aid of grain, being not used reduces polylactic acid mesh number, increase dispersing agent, the method for the processing aids such as lubricant,
It will lead in granulation process and feeding occur and squeeze out difficulty, and the addition of plasticizer will lead to polylactic acid and go out in process
Now degrade, extreme influence Mechanical Properties of Products.
Summary of the invention
The main object of the present invention is to provide a kind of polylactic acid Masterbatch and preparation method thereof, it is intended to realize organic pigment point
Son is combined closely with polylactic acid molecule, increases the firmness of color, and avoid the color transfer of organic pigment at high temperature.
The present invention proposes a kind of polylactic acid Masterbatch, the raw material components including following parts by weight:
100 parts of polylactic acid,
DL- third hands over 10~20 parts of rouge,
0.3~0.6 part of food grade pigment,
0.3~0.6 part of lubrication dispersing agent,
0.2~0.6 part of nucleating agent of compounding,
0.3~0.6 part of chain extender,
6~9 parts of polyvinyl alcohol,
12~16 parts of reinforcing filler.
Preferably, the polylactic acid selects model 3251D polylactic acid, and glass transition temperature is 65 DEG C, melting means 16-
18g/10min。
Preferably, it is 99.6% that the DL- third, which hands over the optical purity of rouge, 95 DEG C of fusing point.
Preferably, the lubrication dispersing agent is EBS, -500 mesh of 200 mesh of partial size.
Preferably, the compounding nucleating agent is two hydrazides of TMC-200 phenyl-phosphonic acid zinc and decanedioic acid diphenyl, in mass ratio
1:1 is compounded.
Preferably, the chain extender is modified chain extender, in mass ratio by BASF chain extender ADR4368 and zinc stearate
1:0.5 is compounded.
Preferably, the molecular weight Mw of the polyvinyl alcohol is 20000-30000.
Preferably, the reinforcing filler is one of talcum powder, nanometer calcium carbonate, montmorillonite, mica powder or any two
The mixture of kind, the talcum powder of the preferred 5000-6000 mesh of talcum powder, the mica of the preferred 3000-5000 mesh of mica powder
Powder.
The present invention proposes a kind of preparation method of polylactic acid Masterbatch again, the polylactic acid Masterbatch that component is made is as above
State described --- 100 parts of polylactic acid, 10~20 parts of rouge of the friendship of DL- third, 0.3~0.6 part of food grade pigment, lubrication dispersing agent 0.3~
0.6 part, 0.2~0.6 part of nucleating agent of compounding, 0.3~0.6 part of chain extender, 6~9 parts of polyvinyl alcohol, 12~16 parts of reinforcing filler,
Preparation method includes the following steps:
(1) first rouge is handed over to be added in the blender slowly to heat up DL- third, opening vacuum pump, 110 DEG C of maximum heating temperature,
Mixing speed 800r/min；
(2) after DL- third hands over rouge to melt completely, addition polyvinyl alcohol, opening vacuum pump, mixing speed 600r/min, when
Between 30min；
(3) food grade pigment is added, opens vacuum pump, mixing speed 1000r/min stirs 20min；Object to be mixed is formed
Stable suspension obtains pigment preparations after realizing the friendship rouge of DL- third to the package of pigment；
(4) it is then again turned on vacuum pump to vacuumize, then be dispersed with stirring uniformly, 102 DEG C of temperature, speed 800r/min,
Time 20min；Object to be mixed forms stable suspension, after realizing the friendship rouge of DL- third to the package of pigment, obtains pre-dispersed face
Material；
(5) polylactic acid, pigment preparations, compounding nucleating agent, lubrication dispersing agent, chain extender, reinforcing filler are sequentially added
High-speed mixer is uniformly mixed, and is then added in parallel dual-screw extruding machine and is squeezed out, draw ratio 1:44, double vacuum evacuations.
The invention has the benefit that
By the present invention in that in two-step method synthesizing polylactic acid performed polymer DL- third hand over rouge, as carrying pigment carrier,
Polyvinyl alcohol protects auxiliary agent as the cladding of pigment, by the effect of chain extension initiator, realizes that DL- third is handed in twin-screw extrusion
Rouge is compound with polylactic acid carrier, the pigment dispersion of Nano grade is realized, using initiator remaining in polylactic acid as pre- point
DL- third hands over the chain carrier of rouge in dispersed pigment, realizes the combination of pigment preparations and polylactic acid molecule, completes organic face
The strong dispersion effect of material.With the cladding and link effect of polyvinyl alcohol, organic pigment is formed and is protected, and reached to polylactic acid
The toughening of material realizes combining closely for organic pigment molecule and polylactic acid molecule, increases the firmness of color, and avoid
The color transfer of organic pigment at high temperature.Pigment dispersion, the polylactic acid that discovery is completed using the present invention are verified by blown film
Masterbatch, the more traditional Masterbatch of dispersion effect have significant increase, and blown film crystal point quantity is by common > 100/m2It is reduced to 1-
10/m2It is a.Phytotoxicity experiments have shown that, this color masterbatch meets 6400 standard of ASTM, verifies mechanical property by cupping machine
Can, show good mechanical performance, heat-resistant experiment shows that heat resisting temperature of the present invention is greater than 100 DEG C.
Production equipment of the present invention is simple, small investment, and raw material are nontoxic degradation material, can be applied to food packet
Dress field, works well, and has large-scale application prospect.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
An a kind of embodiment for polylactic acid Masterbatch and preparation method thereof:
A kind of polylactic acid Masterbatch, the raw material components including following parts by weight:
100 parts of polylactic acid, DL- third hands over 15 parts of rouge, 0.5 part of food grade pigment, 0.5 part of lubrication dispersing agent, compounds nucleating agent
0.5 part, 0.4 part of chain extender, 8 parts of polyvinyl alcohol, 12 parts of reinforcing filler.
Polylactic acid selects model 3251D polylactic acid, and glass transition temperature is 65 DEG C, melting means 16-18g/10min.
DL- third hand over rouge optical purity be 99.6%, 95 DEG C of fusing point.
Food grade pigment includes phthalocyanine blue, phthalocyanine green, and one or more mixing can be used in the pigment such as paratonere.
Lubrication dispersing agent is EBS, -500 mesh of 200 mesh of partial size.
Compounding nucleating agent be two hydrazides of TMC-200 phenyl-phosphonic acid zinc and decanedioic acid diphenyl, 1:1 in mass ratio compounding and
At.
Chain extender is modified chain extender, by BASF chain extender ADR4368 and zinc stearate 1:0.5 in mass ratio compounding
At.
The molecular weight Mw of polyvinyl alcohol is 20000-30000.
Reinforcing filler be one of talcum powder, nanometer calcium carbonate, montmorillonite, mica powder or any two kinds of mixture,
The mixture of preferably talc powder and mica powder is as reinforcing filler, the talcum of the preferred 5000-6000 mesh of talcum powder in the present embodiment
Powder, the mica powder of the preferred 3000-5000 mesh of mica powder.
The preparation method of polylactic acid Masterbatch the following steps are included:
(1) first rouge is handed over to be added in the blender slowly to heat up DL- third, opening vacuum pump, 110 DEG C of maximum heating temperature,
Mixing speed 800r/min；
(2) after DL- third hands over rouge to melt completely, addition polyvinyl alcohol, opening vacuum pump, mixing speed 600r/min, when
Between 30min；
(3) food grade pigment is added, opens vacuum pump, mixing speed 1000r/min stirs 20min；Object to be mixed is formed
Stable suspension obtains pigment preparations after realizing the friendship rouge of DL- third to the package of pigment；
(4) it is then again turned on vacuum pump to vacuumize, then be dispersed with stirring uniformly, 102 DEG C of temperature, speed 800r/min,
Time 20min；Object to be mixed forms stable suspension, after realizing the friendship rouge of DL- third to the package of pigment, obtains pre-dispersed face
Material；
(5) polylactic acid, pigment preparations, compounding nucleating agent, lubrication dispersing agent, chain extender, reinforcing filler are sequentially added
High-speed mixer is uniformly mixed, and is then added in parallel dual-screw extruding machine and is squeezed out, draw ratio 1:44, double vacuum evacuations.
By the present invention in that in two-step method synthesizing polylactic acid performed polymer DL- third hand over rouge, as carrying pigment carrier,
Polyvinyl alcohol protects auxiliary agent as the cladding of pigment, by the effect of chain extension initiator, realizes that DL- third is handed in twin-screw extrusion
Rouge is compound with polylactic acid carrier, the pigment dispersion of Nano grade is realized, using initiator remaining in polylactic acid as pre- point
DL- third hands over the chain carrier of rouge in dispersed pigment, realizes the combination of pigment preparations and polylactic acid molecule, completes organic face
The strong dispersion effect of material.With the cladding and link effect of polyvinyl alcohol, organic pigment is formed and is protected, and reached to polylactic acid
The toughening of material realizes combining closely for organic pigment molecule and polylactic acid molecule, increases the firmness of color, and avoid
The color transfer of organic pigment at high temperature.Pigment dispersion, the polylactic acid that discovery is completed using the present invention are verified by blown film
Masterbatch, the more traditional Masterbatch of dispersion effect have a significant increase, blown film crystal point quantity by common color masterbatch > 100/m2It reduces
For 1-10/m2It is a.Phytotoxicity experiments have shown that, this color masterbatch meets 6400 standard of ASTM, verifies mechanics by cupping machine
Performance, shows good mechanical performance, and heat-resistant experiment shows that heat resisting temperature of the present invention is greater than 100 DEG C.
DL- third hands over the polycondensation reaction of rouge to can use unreacted catalyst in polylactic acid particle, to reduce in particle
Free catalyst.
Production equipment of the present invention is simple, small investment, and raw material are nontoxic degradation material, can apply
It in food packaging applications, works well, has large-scale application prospect.
Experimental data of the invention is as follows:
Polylactic acid Masterbatch is made using the raw material of different proportion in the present invention, and gathers cream made of the raw material by different proportion
Sour Masterbatch carries out dispersibility test, biological degradation rate test, eco-toxicity test, degree of color migration test, value of chromatism
Test, heat resisting temperature test and tensile strength and elongation at break test.
The specific data that the raw material of the different proportion of polylactic acid Masterbatch is made are as shown in the table:
Dispersibility test is carried out to polylactic acid Masterbatch obtained, PBAT material is added in Masterbatch in mass ratio 5%
In, 50 microns of thickness of film is blown out in inflation film manufacturing machine, is subsequently placed under crystal point detector and observes stain and crystal point number.
Biological degradation rate test, according to GB/T 19811-2005 standard testing.
Eco-toxicity test measures barley seed germination percentage according to 13432 standard of EN, and each plate fills sample extremely
Lack 200g and is added in minimum 100 seeds on top.Seed, such as silicon soil sand or perlite are covered with thin layer inert material.
Degree of color migration test, by the PLA thin slice product containing 5% Masterbatch and the thin slice for being not added with Masterbatch
Product is overlapped, and applies the pressure of 1 pounds per square foot in 80 DEG C of baking oven, continues 5 hours, and it is thin that observation is not added with Masterbatch
Result is divided into, non-migratory, slight shift by the appearance of sheet articles by shade, medium migration and serious migration.
Value of chromatism test, obtains product using color difference meter colour examining for the PLA thin slice product containing 5% Masterbatch
Lab value, it is partially yellow compared with standard sample with Δ b value characterization product because organic pigment is easily partially yellow in process
Degree, Δ b value is bigger, shows more yellow using Masterbatch product.
Heat resisting temperature, according to ASTM D648 standard testing.
Tensile strength and elongation at break are tested according to ASTM D638.
Test data is as shown in the table:
Comparison is found after tested, is not added with polyvinyl alcohol in comparative example 1, be cannot achieve to the toughening of polylactic acid and to organic
The protection of pigment, so its toughness is poor, crystal point is more, and Δ b value is larger, and elongation at break is smaller, and color has migration.
Comparative example 2 is not added with DL- third and hands over rouge, causes organic pigment that can not realize good combination with polylactic acid, so its
Crystal point is more, and Δ b value is larger, and color has migration.
Chain extender is not used in comparative example 3, causes Mechanical Properties of Products poor.
Comparative example 4 selects toluene substitution polyvinyl alcohol as auxiliary agent, and reflection, which increases organic solvent, will affect the mechanics of product
Performance and eco-toxicity.
The above is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (9)
1. a kind of polylactic acid Masterbatch, which is characterized in that the raw material components including following parts by weight:
2. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the polylactic acid selects model
3251D polylactic acid, glass transition temperature are 65 DEG C, and melt index is 16-18g/10min under the conditions of 190 DEG C of x10min.
3. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the DL- third hands over the optical purity of rouge
It is 99.6%, 95 DEG C of fusing point.
4. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the lubrication dispersing agent is EBS, partial size
- 500 mesh of 200 mesh.
5. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the compounding nucleating agent is TMC-200
Two hydrazides of phenyl-phosphonic acid zinc and decanedioic acid diphenyl, in mass ratio 1:1 are compounded.
6. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the chain extender is modified chain extender,
It is compounded by BASF chain extender ADR4368 and zinc stearate 1:0.5 in mass ratio.
7. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the molecular weight Mw of the polyvinyl alcohol is
20000-30000。
8. a kind of polylactic acid Masterbatch according to claim 1, which is characterized in that the reinforcing filler is talcum powder, receives
One of rice calcium carbonate, montmorillonite, mica powder or any two kinds of mixture, the preferred 5000-6000 purpose of talcum powder
Talcum powder, the mica powder of the preferred 3000-5000 mesh of mica powder.
9. a kind of preparation method of polylactic acid Masterbatch, which is characterized in that the polylactic acid Masterbatch that component is made is for example above-mentioned
Described in any one of claims 1 to 8, preparation method includes the following steps:
(1) it first hands over rouge to be added in the blender slowly to heat up DL- third, opens vacuum pump, 110 DEG C of maximum heating temperature, stir
Speed 800r/min；
(2) after DL- third hands over rouge to melt completely, polyvinyl alcohol is added, opens vacuum pump, mixing speed 600r/min, time
30min；
(3) food grade pigment is added, opens vacuum pump, mixing speed 1000r/min stirs 20min；
(4) it is then again turned on vacuum pump to vacuumize, then be dispersed with stirring uniformly, 102 DEG C of temperature, speed 800r/min, the time
20min；Object to be mixed forms stable suspension, after realizing the friendship rouge of DL- third to the package of pigment, obtains pigment preparations；
(5) polylactic acid, pigment preparations, compounding nucleating agent, lubrication dispersing agent, chain extender, reinforcing filler are sequentially added into high speed
Mixing machine is uniformly mixed, and is then added in parallel dual-screw extruding machine and is squeezed out, draw ratio 1:44, double vacuum evacuations.
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| CN116065257A (en) * | 2023-01-16 | 2023-05-05 | 广东秋盛资源股份有限公司 | High-color-fastness fiber, and preparation method and application thereof |
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| WO2024000609A1 (en) * | 2022-06-27 | 2024-01-04 | 广东美联新材料股份有限公司 | Color masterbatch with recycled polylactic acid waste as carrier, and preparation method therefor |
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| WO2023103116A1 (en) * | 2021-12-09 | 2023-06-15 | 王玲芝 | Special biomass color masterbatch for degradable plastic and preparation method therefor |
| CN114702804A (en) * | 2022-04-27 | 2022-07-05 | 长兴科隆新材料科技有限公司 | Easily degradable color master batch and preparation method thereof |
| WO2024000609A1 (en) * | 2022-06-27 | 2024-01-04 | 广东美联新材料股份有限公司 | Color masterbatch with recycled polylactic acid waste as carrier, and preparation method therefor |
| CN116065257A (en) * | 2023-01-16 | 2023-05-05 | 广东秋盛资源股份有限公司 | High-color-fastness fiber, and preparation method and application thereof |
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