CN106905673A - A kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier and preparation method thereof - Google Patents
A kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier and preparation method thereof Download PDFInfo
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- 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
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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Abstract
The invention discloses a kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier and preparation method thereof,Methods described is first with terephthalic acid (TPA),Adipic acid and ethylene glycol have synthesized a kind of environment-friendly degradable material PEAT (poly terephthalic acid/ethylene glycol adipate) as the chief component of Masterbatch macromolecule carrier,Then it is PEAT40% 90% according to weight ratio,PLA 5% 25%,Lac resin HY 1% 5%,PPC 2% 15%,Rosin resin TF 100 0.3% 2%,Starch 0 10%,Multi-layer graphene 0 15%,Compatilizer 0.1% 2%,Antioxidant A0.05% 0.2%,Chain extender 0.05% 0.15%,Coupling agent 0.1% 0.5%,Light stabilizer 0.1% 0.3%,Blending extrusion is carried out on screw extruder,Obtain Masterbatch macromolecule carrier.The characteristics of Masterbatch carrier prepared by the present invention not only has that molecular weight is big, is evenly distributed, and with stretching, the excellent mechanical property such as bending strength is high, and the material used in the polymer and extrusion for synthesizing is respectively provided with degradability, belongs to environmentally safe ep-type material.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of synthesis of Masterbatch macromolecule carrier, more particularly to
A kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier and preparation method thereof.
Background technology
With the progress of society, people have requirement higher to plastics, and Masterbatch is so as to more and more be used.So
And there is the defect such as low performance, incompatible existing Masterbatch more, and essentially nondegradable conventional plastic, usage amount is increasingly
Increase, problem of environmental pollution is also gradually notable.Thus, Biodegradable Materials are in terms of existing traditional Masterbatch carrier is substituted
With certain replaceability, the promotion worked environmental protection along with country and the proposition of every policy, it will as not
The neonatal material for coming, possesses vast potential for future development.
But PBS, PLA, PPC, PCL etc. are used alone as degradation material, there is the defect of every aspect, such as
Although PLA material rigidity is strong, mechanical stretch intensity is high, elongation at break is relatively low, not easy processing, be adapted to do sheet material, alloy and
Fiber etc., and later stage degradation is too fast；PPC materials have good processability, but mechanical strength is not high, and glass transition temperature is low；PCL
Then fusing point is low for material, is not suitable for individually doing plastics；PBS materials are then difficult to control synthesis macromolecule two, and relatively costly.Thus need
Synthesize a kind of new biological degradation plastics, so it is modified as the macromolecular material for being adapted to do Masterbatch carrier.
In view of above-mentioned technological deficiency, it is contemplated that obtaining a kind of new macromolecule environment-friendly materials by organic synthesis
PEAT, is, with terephthalic acid (TPA), adipic acid and butanediol as raw material, to choose new catalyst, by controlling technological parameter, is obtained
A kind of new degradable material；Then by blending extrusion test, molecular surface is processed using coupling agent, compatilizer increase
Enter the compatibility between material, the end carboxyl for promoting PEAT, PLA with chain extender continues to participate in reaction, so as to further improve molecule
Amount, and even molecular weight distribution, the addition of lac resin HY, rosin resin TF-100 and multi-layer graphene, then can it is anti-skidding,
The aspects such as increasing stick, protection against the tide, plasticity, mechanical strength and plastics smoothness improve to some extent to material property.Product of the present invention has
Preferably rigidity and stretching higher, bending strength, meet Masterbatch carrier property requirement, the integral material that blending extrusion is obtained
With good mechanical property, safety and environmental protection belongs to environment-friendly degradable material, harmless to environment and human body, has a wide range of application.
Creator of the present invention obtains this creation finally by prolonged research and practice.
The content of the invention
The invention aims to solve shortcoming present in prior art, and a kind of high-tensile for proposing is environmentally friendly
Plastic color master particle macromolecule its preparation method.
To achieve these goals, the present invention propose a kind of high-tensile environmentally-friendly plastic color masterbatch particle macromolecule its preparation
Method, the preparation method includes two steps, and step a adds a certain proportion of ethylene glycol, terephthaldehyde in a kettle.
Acid, adipic acid, warm naturally to 80 DEG C -90 DEG C, add catalyst a, and ladder-elevating temperature carries out esterification to 180 DEG C, until body
Acid number is less than 12mg/g in system, and reaction is complete；Catalyst b and antioxidant B is subsequently adding, ladder-elevating temperature enters to 235 DEG C -245 DEG C
Row is vacuumized polycondensation reaction 2.5-3.5 hours, obtains environment-friendly degradable macromolecular material PEAT (poly terephthalic acids/adipic acid
Glycol ester)；
Step b, weighs PEAT, PLA, lac resin HY, PPC, rosin resin TF-100 according to preset ratio respectively, forms sediment
Powder, multi-layer graphene, compatilizer, antioxidant A, chain extender, coupling agent, light stabilizer, then first by PEAT, lac resin, pine
Botany bar gum, multi-layer graphene and compatilizer hybrid reaction, then all substances are carried out into mixed at high speed uniformly in high-mix mixer,
Extrusion parameter is finally set on screw extruder, blending extrusion is carried out, Masterbatch macromolecule carrier is obtained；
Wherein, described ethylene glycol, terephthalic acid (TPA), the molar ratio of adipic acid are (2.1-4.2)：1：(0.5-2)；Institute
The catalyst a consumptions stated are 0.2 ‰ -0.6 ‰；Described catalyst b consumptions are 0.4 ‰ -1.4 ‰；Described antioxidant B consumptions
It is 0.5 ‰ -3 ‰；Described Esterification Stage ladder-elevating temperature mode is warming up to 150 by 90 DEG C for the design temperature of reactor by 1h
DEG C, after stabilization reaction 0.5h, continue to heat up, 170 DEG C are warming up to by 1h, stabilization reaction 1h continues to heat up, and is warming up to by 2h
180℃；Described polycondensation phase ladder-elevating temperature mode is warming up to 190 DEG C by 180 DEG C for the design temperature of reactor by 2h, so
Afterwards 235-245 DEG C is to slowly warm up to by 3h；
Described each component weight ratio is PEAT40%-90%, PLA 5%-25%, lac resin HY1%-5%, PPC
2%-15%, rosin resin TF-100 0.3%-2%, starch 0-10%, multi-layer graphene 0-15%, compatilizer 0.1%-
2%, antioxidant A 0.05%-0.2%, chain extender 0.05%-0.15%, coupling agent 0.1%-0.5%, light stabilizer 0.1%-
0.3%；
For first be placed in for raw material by described PEAT, lac resin, rosin resin, multi-layer graphene and compatilizer hybrid reaction
In 70 DEG C of vacuum drying ovens, persistently dry 5 hours, then press PEAT, lac resin, rosin resin and multi-layer graphene
According to preset ratio addition reactor, while rising high-temperature to 180 DEG C, the compatilizer of proper ratio, stirring are added at a temperature of this
Reaction 1.5-2 hours, discharging；
Each section of temperature of described screw extruder be set as 158 DEG C -165 DEG C, 160 DEG C -170 DEG C, 160 DEG C -175 DEG C,
170 DEG C -190 DEG C, 170 DEG C -190 DEG C, 175 DEG C -195 DEG C, 165 DEG C -180 DEG C, rotating speed is to be determined according to the actual conditions of material.
Further, in the catalyst that described catalyst a is combined with organic tin respectively for cobalt acetate, nickel acetate one
Kind；Described catalyst b be organotitanium, organic guanidine in one or two；Described antioxidant B is 168 and 126
Compound or 626 and 1010 compound.
Further, described compatilizer is the one kind in GMA, G-ADR；Described antioxidant A is 264,1010,1098
In one kind；Described chain extender NPPN-638S, NPPN-631；Described coupling agent is γ-diethylenetriamine hydroxypropyl methyl two
At least one in methoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, tetraethoxysilane；Described light stabilization
Agent is the one kind in O-hydroxyl-diphenyl ketone, salicylate, s-triazine.
Further, described cobalt acetate and organic tin compound are that cobalt acetate is first melted into ethylene glycol, then slowly
Organic tin is added, after being heated to reflux 3 hours, a large amount of solvent gained bottom products is rotated out；Described nickel acetate and organotin
Class compound adds NaOH as catalyst for nickel acetate is uniformly dispersed with toluene first, is slow added into ethylenediamine
Tetrem acid solution, carries out high temperature reflux reacts 5 hours, is then dehydrated with toluene, changes reaction unit, removes toluene, and residue is produced
Thing is with organic tin catalyst according to 1:1 ratio is well mixed, and nickel acetate and organic tin composite catalyst is obtained；Described
Organotitanium is the one kind in the monooctyl ester of metatitanic acid four, poly- tetra-n-butyl titanate, KRTi-1；Described organic guanidine is guanidine radicals second
One kind in acid, methylguanidine hydrochloride；168 described and 126 compound be 60% 168 and 40% 126；Described
626 and 1010 compounds be 20% 626 and 80% 1010.
Further, described G-ADR is first in 500mL there-necked flasks, to add 126g melamine powders, is poured into
The 1-METHYLPYRROLIDONE of 200mL, is allowed to dispersed, and 70-80 DEG C is heated to while stirring；Then 31.5g toluene two is taken
Isocyanates, is slowly added dropwise into there-necked flask, continues to stir and be warming up to 135-140 DEG C；Finally measure 60g styrene and
92g methyl methacrylates, mixing is scattered in 100mLN- methyl pyrrolidones, adds melamine to disperse with pressure funnel long
In liquid, continue to react 6h, obtain compatilizer G-ADR.
Further, described organic tin catalyst be one kind in dibutyl tin, stannous octoate, Tricyclohexyltin or
It is various.
The present invention also provides a kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier, including：Environment-friendly degradable material
Material PEAT compositions, Masterbatch carrier components, described PEAT to add a certain proportion of ethylene glycol, to benzene in a kettle. first
Dioctyl phthalate, adipic acid, warm naturally to 80 DEG C -90 DEG C, add catalyst a, and ladder-elevating temperature carries out esterification to 180 DEG C, directly
Acid number is less than 12mg/g into system, and reaction is complete；Catalyst b and antioxidant B is subsequently adding, ladder-elevating temperature is to 235 DEG C -245
DEG C, vacuumize polycondensation reaction 2.5-3.5 hours, PEAT is obtained；Described carrier component is PEAT40%-90%, PLA
5%-25%, lac resin HY 1%-5%, PPC 2%-15%, rosin resin TF-100 0.3%-2%, starch 0-10%,
Multi-layer graphene 0-15%, compatilizer 0.1%-2%, antioxidant A 0.05%-0.2%, chain extender 0.05%-0.15% are even
Connection agent 0.1%-0.5%, light stabilizer 0.1%-0.3%.
Compared with prior art, it is of the invention by synthesizing a kind of degradable environment-friendly material PEAT, as the important set of carrier
Into part；Contain aromatic structure in PEAT (poly terephthalic acid/ethylene glycol adipate) molecule segment, make whole macromolecular
Show excellent mechanical property；With aliphatic segment is inlayed in molecular configurational, aliphatic structure is present in molecular structure
In promote the plastics can completely to resolve into carbon dioxide and water in its natural state.
Why PEAT materials are the transparent material with excellent mechanical performance, are the fragrance due to containing in molecular structure
Race's structure belongs to polar material, and molecule segment is symmetrical structure after polymerization, and intermolecular force is big, thus shows preferably just
Property embrittlement；And after adding aliphatic structure, the regularity of saboteur that not only can be appropriate increases the toughness of molecule, and
The crystallinity of molecule can be changed, crystalline rate is reduced, so as to show as transparent or semitransparent material.Although aromatic structure
Polyester does not possess good biological degradability, but for PEAT, because containing aliphatic poly ester structure in its macromolecular chain segment,
Aliphatic is easily decomposed under field conditions (factors), causes PEAT macromoleculars to be quickly converted to lower-molecular substance, such that it is able to accelerate it
Decomposition rate, until originally resolving into water and carbon dioxide, and makes it have totally biodegradable.
In addition, another Main Ingredients and Appearance PLA in intermingling material is used as degradation material, while having mechanicalness higher concurrently
Can, tensile strength is high, can also improve the overall mechanical properties of carrier.The other components of blending such as PPC, starch, falling within to drop
Solution material, under field conditions (factors), by solar radiation, wet environment or microbial decomposition, macromolecular structure gradually by
Broken ring, becomes a large amount of low molecule segments, and these low molecule segments are easily decomposed by Institute of Micro-biology, are eventually converted into water, dioxy
Change carbon, biomass etc., the improvement of lac, rosin, multi-layer graphene to material property plays a significant role, and belongs to natural material,
Such material environmental sound.Thus other Matter Compositions fall within environmentally friendly material, thus this hair in Masterbatch carrier
The Masterbatch macromolecule carrier of bright preparation not only has high-tensile, and with environment-friendly degradable.
In the present invention, the addition of multi-layer graphene is relative to be increased, and will effectively using the laminated structure of graphite can be synthesized
Polyester material, lac resin and rosin resin and other materials preferably can merge in the middle of laminated structure, be interspersed in
In multi-layer graphene, so as to form the macromolecular structure of puffy on apparent, then can further expand on molecular structure point
Son amount, strengthens mechanical property；Further, since multi-layer graphene has good intensity and pliability concurrently in itself, thus improving color
Master batch carrier mechanical strength aspect has remarkable effect, and plastics will not be caused to become fragile again.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.
Embodiment 1
A certain proportion of 105mol ethylene glycol, 50mol terephthalic acid (TPA)s, 30mol adipic acids are added in a kettle., it is natural
It is warming up to 80 DEG C -90 DEG C, adds 0.3 ‰ nickel acetates and dibutyl tin compound, ladder-elevating temperature carries out esterification to 180 DEG C,
Until reaction is complete, now acid number is 11.9mg/g；It is subsequently adding 0.6 ‰ glycocyamines and 1 ‰ 1010 and 626 compounds, rank
Ladder is warming up to 240 DEG C, carries out vacuumizing polycondensation reaction 2.5 hours, you can obtain macromolecule PEAT；
In the present embodiment, described nickel acetate is that nickel acetate is uniformly dispersed with toluene first with dibutyl tin compound,
Add NaOH as catalyst, be slow added into edta solution, carry out high temperature reflux reacts 5 hours, be used to
Synthesize the ethylenediamine tetra-acetic acid chelate of metallic nickel, thus the surface area of catalyst can be effectively increased, so as in esterification
Middle increase catalytic rate, and nickel ion in chelate has free property higher, can more uniformly be scattered in polyester
In performed polymer, reaction forward is promoted to carry out.
In above process, be dehydrated with toluene, change reaction unit, remove toluene, resultant product and dibutyl tin according to
1:1 ratio is well mixed, and is, using the high activity of tin catalyst, to substitute part Raney nickel, both can guarantee that heavy metal
Usage amount is not exceeded, and reaction balance can be promoted quickly to move right again.
In the present embodiment, described Esterification Stage ladder-elevating temperature mode for reactor design temperature by 90 DEG C by 1h liters
Temperature is stablized after reacting 0.5h to 150 DEG C, because now esterification has begun to, because reactant concentration is higher in system,
Can be reacted under moieties low temperature, be formed initial performed polymer.
In above process, continue to heat up, 170 DEG C are warming up to by 1h, stabilization reaction 1h continues to heat up, by 2h liters
Temperature is to 180 DEG C, it is ensured that the slow of reaction is carried out, and prevents reaction too fast, the situation of carboxy blocking is caused, due to the boiling point of ethylene glycol
It it is 197.3 DEG C, a small amount of water produced with esterification can form azeotropic system, thus azeotropic point is slightly below 197 DEG C, and temperature sets
It is set to 180 DEG C, can both ensures being smoothed out for esterification, can avoids temperature too high again and ethylene glycol is steamed system.
In the present embodiment, described polycondensation phase ladder-elevating temperature mode for reactor design temperature by 180 DEG C by 2h
190 DEG C are warming up to, this stage steams with moisture, azeotropic point is raised, and at a temperature of this, ethylene glycol is difficult to steam system, high temperature
Environment can be such that esterification further occurs, it is ensured that the completeness of extent of reaction.
In above process, it is to slowly warm up to 235-245 DEG C by 3h, designs slower programming rate, on the one hand can be with
Ensure that performed polymer further occurs chain reaction, on the other hand because polycondensation reaction is carried out in vacuum systems, initial stage
Reaction system belongs to vacuum Unstable Systems, in continuous vacuum, if intensification is too fast, can cause small-molecule substance
System is steamed, and influences the synthesis of macromolecular, or even block vacuum system, cause reaction to fail.
Precise PEAT57.5%, PLA15%, lac resin HY2%, PPC15%, rosin resin TF-100
0.5%, starch 9%, multi-layer graphene 0.1%, GMA 0.3%, 264 0.1%, NPPN-638S 0.1%, γ-divinyl three
Amine hydroxypropyl methyl dimethoxysilane 0.3%, salicylate 0.1%, first by PEAT, lac resin, rosin resin, Multi-layer graphite
Alkene and compatilizer hybrid reaction, then all substances are carried out into mixed at high speed uniformly in high-mix mixer, it is standby；
Each section of temperature of screw extruder is set as 165 DEG C, 168 DEG C, 168 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 175 DEG C,
Rotating speed is 45kg/h, and blending extrusion obtains Masterbatch macromolecule carrier.
Embodiment 2
A certain proportion of 135mol ethylene glycol, 50mol terephthalic acid (TPA)s, 50mol adipic acids are added in a kettle., it is natural
80 DEG C -90 DEG C are warming up to, add the compound of 0.4 ‰ zinc acetates and stannous octoate, ladder-elevating temperature to carry out being esterified instead to 180 DEG C
Should, until reaction is complete, now acid number is 11.7mg/g；It is subsequently adding 0.4 ‰ glycocyamines and 0.8 ‰ 1010 and 626 compoundings
Thing, ladder-elevating temperature carries out vacuumizing polycondensation reaction 2.5 hours, you can obtain macromolecule PEAT to 240 DEG C；
Precise PEAT60.25%, PLA5%, lac resin HY4%, PPC10%, rosin resin TF-100 1%,
Starch 4%, multi-layer graphene 15%, GMA 0.2%, 1,098 0.1%, NPPN-631 0.1%, tetraethoxysilane
0.25%, triazines 0.1%, first by PEAT, lac resin, rosin resin, multi-layer graphene and compatilizer hybrid reaction, then will
All substances carry out mixed at high speed uniformly in high-mix mixer, standby；
Each section of temperature of screw extruder is set as 158 DEG C, 162 DEG C, 165 DEG C, 172 DEG C, 178 DEG C, 180 DEG C, 170 DEG C,
Rotating speed is 65kg/h, and blending extrusion obtains Masterbatch macromolecule carrier.
In the present embodiment, described lac resin HY4%, rosin resin TF-100 1%, multi-layer graphene 15%, multilayer
The addition of Graphene is relative to be increased, can effectively using the laminated structure of graphite, the polyester material that will synthesize, lac resin and
Rosin resin and other materials can be merged preferably in the middle of laminated structure, be interspersed in multi-layer graphene, so as in table
The macromolecular structure of puffy is formed in sight, molecular weight then can be further expanded on molecular structure, strengthen mechanical property；Separately
Outward, good intensity and pliability is had concurrently in itself due to multi-layer graphene, thus in terms of Masterbatch carrier mechanical strength is improved
With remarkable effect, plastics will not be caused to become fragile again.
Embodiment 3
A certain proportion of 155mol ethylene glycol, 40mol terephthalic acid (TPA)s, 80mol adipic acids are added in a kettle., it is natural
80 DEG C -90 DEG C are warming up to, the compound of 0.5 ‰ nickel acetates and stannous octoate is added, it is anti-that ladder-elevating temperature starts esterification to 180 DEG C
Should, until reaction is complete, now acid number is 11.7mg/g；0.6 ‰ glycocyamines and 2 ‰ 168 and 126 compounds are subsequently adding,
Ladder-elevating temperature carries out vacuumizing polycondensation reaction 2.5 hours, you can obtain macromolecule PEAT to 245 DEG C；
Precise PEAT75%, PLA5%, lac resin HY3%, PPC8%, rosin resin TF-100 2%, starch
5%, multi-layer graphene 0.8%, G-ADR 0.15%, 1,010 0.2%, the NPPN-631 0.15%, ('beta '-methoxy of vinyl three
Ethyoxyl) silane 0.42%, O-hydroxyl-diphenyl ketone 0.3%, first by PEAT, lac resin, rosin resin, multi-layer graphene and
Compatilizer hybrid reaction, then all substances are carried out into mixed at high speed uniformly in high-mix mixer, it is standby；
In the present embodiment, described compatilizer G-ADR is first in 500mL there-necked flasks, to add 126g melamines
Powder, pours into the 1-METHYLPYRROLIDONE of 200mL, is allowed to dispersed, and 70-80 DEG C is heated to while stirring；Then take
31.5g toluene di-isocyanate(TDI)s, are slowly added dropwise into there-necked flask, continue to stir and be warming up to 135-140 DEG C；Finally measure
60g styrene and 92g methyl methacrylates, mixing are scattered in 100mLN- methyl pyrrolidones, and three are added with pressure funnel long
In poly cyanamid dispersion liquid, continue to react 6h, be obtained.It is the material based on melamine, functional group one of first and first
Phenylene diisocyanate reacts, and then carries out polymerisation with styrene and methyl methacrylate, obtains the ring with amido
Oxygen system product, can carry out Quick cross-linking reaction, so that compatible between changing material in co-mixing system with many kinds of substance
Property.
Each section of temperature of screw extruder is set as 160 DEG C, 163 DEG C, 165 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C,
Rotating speed 40kg/h, blending extrusion obtains Masterbatch macromolecule carrier.
Embodiment 4
A certain proportion of 125mol ethylene glycol, 40mol terephthalic acid (TPA)s, 60mol adipic acids are added in a kettle., it is natural
80 DEG C -90 DEG C are warming up to, add the compound of 0.25 ‰ zinc acetates and Tricyclohexyltin, ladder-elevating temperature to start to be esterified to 180 DEG C
Reaction, until reaction is complete, now acid number is 11.8mg/g；1 ‰ methylguanidine hydrochlorides and 3 ‰ 1010 and 626 are subsequently adding to answer
With thing, ladder-elevating temperature carries out vacuumizing polycondensation reaction 2.5 hours, you can obtain macromolecule PEAT to 235 DEG C；
Precise PEAT87.15%, PLA8%, lac resin HY1%, PPC2%, rosin resin TF-100 1%, G-
ADR 0.15%, 1,010 0.1%, NPPN-638S 0.1%, vinyl three ('beta '-methoxy ethyoxyl) silane 0.3%, adjacent hydroxyl
Base benzophenone 0.2%, first by PEAT, lac resin, rosin resin, multi-layer graphene and compatilizer hybrid reaction, then by institute
Have material carries out mixed at high speed uniformly in high-mix mixer, standby；
Each section of temperature of screw extruder is set as 158 DEG C, 163 DEG C, 165 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C,
Rotating speed 60kg/h, blending extrusion obtains Masterbatch macromolecule carrier.
Comparative example 1
Precise PE99%, G-ADR 0.1%, 1,010 0.1%, the NPPN-631 0.1%, (beta-methoxy of vinyl three
Base oxethyl) silane 0.35%, O-hydroxyl-diphenyl ketone 0.35%, and be well mixed, it is standby；
Each section of temperature of screw extruder is set as 160 DEG C, 163 DEG C, 165 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C,
Rotating speed 40kg/h, blending extrusion obtains Masterbatch macromolecule carrier.
Comparative example 2
Precise PE76%, PLA5%, lac resin HY3%, PPC8%, rosin resin TF-100 2%, starch
5%, GMA 0.15%, 1,010 0.2%, NPPN-631 0.15%, vinyl three ('beta '-methoxy ethyoxyl) silane 0.2%,
O-hydroxyl-diphenyl ketone 0.3%, and be well mixed, it is standby；
Each section of temperature of screw extruder is set as 160 DEG C, 163 DEG C, 165 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C,
Rotating speed 40kg/h, blending extrusion obtains Masterbatch macromolecule carrier.
By to it is above-mentioned be that the product that embodiment and comparative example are obtained carries out Mechanics Performance Testing, obtain following result, see
Table 1
The embodiment of table 1 carries out Mechanics Performance Testing and degradation property test with comparative example
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (7)
1. a kind of high-tensile environmentally-friendly plastic color masterbatch particle macromolecule its preparation method, it is characterised in that the preparation method bag
Two steps are included,
Step a, adds a certain proportion of ethylene glycol, terephthalic acid (TPA), adipic acid in a kettle., warms naturally to 80 DEG C -90
DEG C, add catalyst a, ladder-elevating temperature to carry out esterification to 180 DEG C, until acid number is less than 12mg/g in system, reaction is complete；
Catalyst b and antioxidant B is subsequently adding, ladder-elevating temperature to 235 DEG C -245 DEG C vacuumize polycondensation reaction 2.5-3.5 hours,
Obtain environment-friendly degradable macromolecular material PEAT (poly terephthalic acid/ethylene glycol adipate)；
Step b, weighs PEAT according to preset ratio respectively, and PLA, lac resin HY, PPC, rosin resin TF-100, starch is more
Layer graphene, compatilizer, antioxidant A, chain extender, coupling agent, light stabilizer, then first by PEAT, lac resin, rosin tree
Fat, multi-layer graphene and compatilizer hybrid reaction, then all substances are carried out into mixed at high speed uniformly in high-mix mixer, finally
Extrusion parameter is set on screw extruder, blending extrusion is carried out, Masterbatch macromolecule carrier is obtained；
Wherein, described ethylene glycol, terephthalic acid (TPA), the molar ratio of adipic acid are (2.1-4.2)：1：(0.5-2)；Described
Catalyst a consumptions are 0.2 ‰ -0.6 ‰；Described catalyst b consumptions are 0.4 ‰ -1.4 ‰；Described antioxidant B consumptions are
0.5‰-3‰；Described Esterification Stage ladder-elevating temperature mode is warming up to 150 by 90 DEG C for the design temperature of reactor by 1h
DEG C, after stabilization reaction 0.5h, continue to heat up, 170 DEG C are warming up to by 1h, stabilization reaction 1h continues to heat up, and is warming up to by 2h
180℃；Described polycondensation phase ladder-elevating temperature mode is warming up to 190 DEG C by 180 DEG C for the design temperature of reactor by 2h, so
Afterwards 235-245 DEG C is to slowly warm up to by 3h；
Described each component weight ratio is PEAT40%-90%, PLA 5%-25%, lac resin HY1%-5%, PPC 2%-
15%, rosin resin TF-1000.3%-2%, starch 0-10%, multi-layer graphene 0-15%, compatilizer 0.1%-2%, antioxygen
Agent A 0.05%-0.2%, chain extender 0.05%-0.15%, coupling agent 0.1%-0.5%, light stabilizer 0.1%-0.3%；
Described PEAT, lac resin, rosin resin, multi-layer graphene and compatilizer hybrid reaction by raw material to be first placed in 70 DEG C
In vacuum drying oven, persistently dry 5 hours, then by PEAT, lac resin, rosin resin and multi-layer graphene according to pre-
If ratio is added in reactor, while rising high-temperature to 180 DEG C, the compatilizer of proper ratio, stirring reaction are added at a temperature of this
1.5-2 hours, discharging；
Each section of temperature of described screw extruder be set as 158 DEG C -165 DEG C, 160 DEG C -170 DEG C, 160 DEG C -175 DEG C, 170
DEG C -190 DEG C, 170 DEG C -190 DEG C, 175 DEG C -195 DEG C, 165 DEG C -180 DEG C, rotating speed is to be determined according to the actual conditions of material.
2. high-tensile environmentally-friendly plastic color masterbatch particle macromolecule preparation method according to claim 1, it is characterised in that institute
The catalyst a for stating is the one kind in the catalyst that cobalt acetate, nickel acetate are combined with organic tin respectively；Described catalyst b is
One or two in organotitanium, organic guanidine；Described antioxidant B is 168 and 126 compounds or 626 Hes
1010 compound.
3. high-tensile environmentally-friendly plastic color masterbatch particle macromolecule its preparation method according to claim 1, it is characterised in that
Described compatilizer is the one kind in GMA, G-ADR；Described antioxidant A is the one kind in 264,1010,1098；Described expansion
Chain agent NPPN-638S, NPPN-631；Described coupling agent is γ-diethylenetriamine hydroxypropyl methyl dimethoxysilane, vinyl
At least one in three ('beta '-methoxy ethyoxyl) silane, tetraethoxysilane；Described light stabilizer is o-hydroxy benzophenone
One kind in ketone, salicylate, s-triazine.
4. high-tensile environmentally-friendly plastic color masterbatch particle macromolecule its preparation method according to claim 2, it is characterised in that
Described cobalt acetate and organic tin compound are that cobalt acetate is first melted into ethylene glycol, are then slowly added into organic tin, are heated
After backflow 3 hours, a large amount of solvent gained bottom products are rotated out；Described nickel acetate is first by second with organic tin compound
Sour nickel is uniformly dispersed with toluene, adds NaOH as catalyst, is slow added into edta solution, carries out high temperature
Back flow reaction 5 hours, is then dehydrated with toluene, changes reaction unit, removes toluene, and resultant product is pressed with organic tin catalyst
According to 1:1 ratio is well mixed, and nickel acetate and organic tin composite catalyst is obtained；Described organotitanium is metatitanic acid four
One kind in monooctyl ester, poly- tetra-n-butyl titanate, KRTi-1；During described organic guanidine is glycocyamine, methylguanidine hydrochloride
It is a kind of；168 described and 126 compound be 60% 168 and 40% 126；626 and 1010 described compounds are 20%
626 and 80% 1010.
5. high-tensile environmentally-friendly plastic color masterbatch particle macromolecule preparation method according to claim 3, it is characterised in that institute
The G-ADR for stating is first in 500mL there-necked flasks, to add 126g melamine powders, pours into the N- crassitudes of 200mL
Ketone, is allowed to dispersed, and 70-80 DEG C is heated to while stirring；Then 31.5g toluene di-isocyanate(TDI)s are taken, be slowly added dropwise to
In there-necked flask, continue to stir and be warming up to 135-140 DEG C；60g styrene and 92g methyl methacrylates are finally measured, is mixed
Conjunction is scattered in 100mLN- methyl pyrrolidones, with pressure funnel addition melamine dispersion liquid long, continues to react 6h, is obtained
Compatilizer G-ADR.
6. the high-tensile environmentally-friendly plastic color masterbatch particle macromolecule its preparation method according to claim 2 or 4, its feature exists
In described organic tin catalyst is one or more in dibutyl tin, stannous octoate, Tricyclohexyltin.
7. a kind of high-tensile environmentally-friendly plastic Masterbatch macromolecule carrier, it is characterised in that including environment-friendly degradable material
PEAT compositions, Masterbatch carrier components, described PEAT to add a certain proportion of ethylene glycol, to benzene two in a kettle. first
Formic acid, adipic acid, warm naturally to 80 DEG C -90 DEG C, add catalyst a, and ladder-elevating temperature carries out esterification to 180 DEG C, until
Acid number is less than 12mg/g in system, and reaction is complete；Be subsequently adding catalyst b and antioxidant B, ladder-elevating temperature to 235 DEG C -245 DEG C,
Vacuumize polycondensation reaction 2.5-3.5 hours, PEAT is obtained；Described carrier component is PEAT40%-90%, PLA 5%-
25%, lac resin HY 1%-5%, PPC 2%-15%, rosin resin TF-1000.3%-2%, starch 0-10%, multilayer
Graphene 0-15%, compatilizer 0.1%-2%, antioxidant A 0.05%-0.2%, chain extender 0.05%-0.15%, coupling agent
0.1%-0.5%, light stabilizer 0.1%-0.3%.
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