CN107501881A - The composite of trapping environmental protection, preparation method and applications - Google Patents
The composite of trapping environmental protection, preparation method and applications Download PDFInfo
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Abstract
The present invention relates to degradation plastic field, specifically, there is provided a kind of composite of trapping environmental protection, preparation method and applications.The composite of the trapping environmental protection is mainly prepared by the raw material of following parts by weight：13 parts of 20 60 parts of PLA, 20 40 parts of PBAT, 5 20 parts of poly (propylene carbonate), 1 10 parts of PLA/ Nano titanium nitrides master batch, 3 15 parts of filler, 15 parts of thermoplastic elastomer (TPE), 0.5 1 parts of lubricant and chain extender；The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：0.5 1.5 parts of 80 120 parts of PLA, 0.3 1.2 parts of Nano titanium nitride, 0.3 1.2 parts of stabilisers against hydrolysis and chain extender.The composite has that the feature of environmental protection is good, gas barrier rate is high, heat endurance is good and the advantages of good mechanical property.
Description
Technical field
The present invention relates to degradation plastic field, composite, preparation method in particular to a kind of trapping environmental protection
And its application.
Background technology
PLA (PLA) is a kind of new bio-based and Biodegradable material, using reproducible plant resources (such as
Corn) starch material that is proposed is made.Starch material obtains glucose via saccharification, then is sent out by glucose and certain strain
The lactic acid of high-purity is made in ferment, then the PLA of certain molecular weight is synthesized by chemical synthesis process；It has good biology
Degradability, can be degradable under given conditions by microorganism in nature after use, ultimately generates carbon dioxide and water, no
Environment is polluted, this is highly beneficial to environmental protection, is generally acknowledged environment-friendly material.
The heat endurance of PLA is good, 170~230 DEG C of processing temperature, the solvent resistance having had, can be carried out with various ways
Processing, such as extruding, spinning, biaxial stretch-formed, injection-blow molding.Product is in addition to energy is biodegradable made of PLA, bio-compatible
Property, glossiness, the transparency, feel and heat-resist, also with certain fungus resistance, anti-flammability and ultraviolet-resistent property, therefore purposes
It is quite varied, it can be used as packaging material, fiber and non-woven fabric etc., be currently used primarily in packaging (shopping bag, preservative film), clothes
The field such as (underwear, coat), industry (building, agricultural, forestry, papermaking) and health care.
With the growth of field of food preservation demand, PLA as a kind of green preservative film material by extensive concern,
But the gas barrier property of its material in itself is slightly worse, can not meet fresh-keeping function.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of composite of trapping environmental protection, and the composite is with PLA and PLA/
Nano titanium nitride master batch is primary raw material, and not only the feature of environmental protection is good, moreover it is possible to effectively obstructs gas, while also ensures composite
The mechanical performance such as heat endurance and tensile strength and elongation at break is not suffered a loss, and Product processing is functional.
The second object of the present invention is to provide a kind of preparation method of the composite of trapping environmental protection, the letter of this method technique
It is single, easily operated, controllable degree is high, is adapted to produce in enormous quantities, the composite of the trapping that is obtained using this method environmental protection is had
The feature of environmental protection is good, gas barrier rate is high, heat endurance is good and the advantages of good mechanical property.
The third object of the present invention is to provide a kind of composite of above-mentioned trapping environmental protection in plastic foil, polybag, modeling
Application in magazine or plastic bottle, above-mentioned plastic product have that the feature of environmental protection is good, gas barrier rate is high, heat endurance is good and mechanicalness
Can be good the advantages of.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, the invention provides a kind of composite of trapping environmental protection, mainly by the raw material system of following parts by weight
It is standby to form：PLA 20-60 parts, PBAT 20-40 parts, poly (propylene carbonate) 5-20 parts, PLA/ Nano titanium nitride master batch 1-10 parts,
Filler 3-15 parts, thermoplastic elastomer (TPE) 1-5 parts, lubricant 0.5-1 parts and chain extender 1-3 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80-120 parts, receive
Rice titanium nitride 0.3-1.2 parts, stabilisers against hydrolysis 0.3-1.2 parts and chain extender 0.5-1.5 parts.
As further preferably technical scheme, the composite is mainly prepared by the raw material of following parts by weight：
PLA 30-50 parts, PBAT 24-36 parts, poly (propylene carbonate) 6-18 parts, PLA/ Nano titanium nitride master batch 2-8 parts, filler 5-12
Part, thermoplastic elastomer (TPE) 2-5 parts, lubricant 0.6-1 parts and chain extender 1.2-2.8 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 84-106 parts, receive
Rice titanium nitride 0.3-1.0 parts, stabilisers against hydrolysis 0.3-1.0 parts and chain extender 0.6-1.4 parts.
As further preferably technical scheme, the composite is mainly prepared by the raw material of following parts by weight：
PLA 35-45 parts, PBAT 28-32 parts, poly (propylene carbonate) 8-14 parts, PLA/ Nano titanium nitride master batch 3-7 parts, filler 7-10
Part, thermoplastic elastomer (TPE) 2-4 parts, lubricant 0.6-0.9 parts and chain extender 1.4-2.6 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 88-102 parts, receive
Rice titanium nitride 0.3-0.8 parts, stabilisers against hydrolysis 0.3-0.8 parts and chain extender 0.8-1.2 parts.
As further preferably technical scheme, the PLA/ Nano titanium nitrides master batch is mainly by PLA and modified nanometer
Titanium nitride is prepared, and the Nano titanium nitride of the modification is mainly prepared by Nano titanium nitride and silane coupler, described
Silane coupler is the 0.03-3wt.% of the Nano titanium nitride.
As further preferably technical scheme, the silane coupler is at least one in KH550, KH560 or KH570
Kind.
As further preferably technical scheme, the thermoplastic elastomer (TPE) be SBG, POE-g-GMA or MBS at least
It is a kind of.
Second aspect, the invention provides a kind of preparation method of the composite of above-mentioned trapping environmental protection, including following step
Suddenly：
(a) it is granulated and obtains after being well mixed the PLA of formula ratio, Nano titanium nitride, stabilisers against hydrolysis and chain extender
PLA/ Nano titanium nitride master batches；
(b) by PLA/ Nano titanium nitrides master batch, PLA, PBAT, poly (propylene carbonate), filler, the thermoplastic elastic of formula ratio
It is granulated after body, lubricant and chain extender are well mixed and obtains the composite of the trapping environmental protection.
As further preferably technical scheme, the Nano titanium nitride first passes around modification, and processing method is：It is first
The silane coupler of formula ratio and alcohol and water are first configured to solution of silane, then by the Nano titanium nitride of formula ratio and the silicon
Dried after alkane solution is well mixed.
As further preferably technical scheme, the granulation in step (a) is double-screw extruding pelletizing, the temperature of twin-screw
For 165-175 DEG C；Granulation in step (b) is double-screw extruding pelletizing, and the temperature of twin-screw is 165-180 DEG C.
The third aspect, the invention provides a kind of composite of above-mentioned trapping environmental protection in plastic foil, polybag, plastic casing
Or the application in plastic bottle.
Compared with prior art, beneficial effects of the present invention are：
The composite of trapping environmental protection provided by the invention is prepared by primary raw material of PLA and PLA/ Nano titanium nitrides master batch
Form, scientific formulation, by the reasonable cooperation of each raw material, given full play to the gas barrier advantage and PLA of nano-titanium oxide
Degradable advantage, not only the feature of environmental protection is good for obtained composite, moreover it is possible to effectively obstructs gas, OTR oxygen transmission rate ratio is without nanometer nitrogen
Change the compound PLA of titanium low 8%-25%, while also ensure that the heat endurance of composite and tensile strength and fracture are stretched
The mechanical performances such as long rate are not suffered a loss, and Product processing is functional.
The preparation method technique of the composite of trapping provided by the invention environmental protection is simple, easily operated, controllable degree is high,
It is adapted to produce in enormous quantities, the composite of the trapping that obtains using this method environmental protection has that the feature of environmental protection is good, gas barrier rate is high, heat
Stability is good and the advantages of good mechanical property.
The composite of above-mentioned trapping environmental protection is applied in plastic foil, polybag, plastic casing or plastic bottle, can be made
Stating plastic product has that the feature of environmental protection is good, gas barrier rate is high, heat endurance is good and the advantages of good mechanical property.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.
In a first aspect, the invention provides a kind of composite of trapping environmental protection, mainly by the raw material system of following parts by weight
It is standby to form：PLA 20-60 parts, PBAT 20-40 parts, poly (propylene carbonate) 5-20 parts, PLA/ Nano titanium nitride master batch 1-10 parts,
Filler 3-15 parts, thermoplastic elastomer (TPE) 1-5 parts, lubricant 0.5-1 parts and chain extender 1-3 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80-120 parts, receive
Rice titanium nitride 0.3-1.2 parts, stabilisers against hydrolysis 0.3-1.2 parts and chain extender 0.5-1.5 parts.
PLA (Polylactic acid, PLA) is the polymer obtained using lactic acid as main polymerizable raw material, and raw material comes
Source is abundant and can regenerate.The production process of PLA is pollution-free, and product can be biodegradable, realizes in nature
Circulation, therefore be preferable Green Polymer Material.In the composite of the present invention, count in parts by weight, PLA is typical but non-
Restricted content is：20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44
Part, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts or 60 parts.
PBAT (Poly (butyleneadipate-co-terephthalate), polyadipate/terephthalic acid (TPA) fourth two
Ester) existing preferably ductility and elongation at break, also there are preferable heat resistance and impact property；In addition, also have excellent
Biological degradability, it is that one of best degradable material is applied in very active and market in current biodegradable plastic research.The present invention
Composite in, count in parts by weight, the typical but non-limiting contents of PBAT are：20 parts, 22 parts, 24 parts, 26 parts, 28
Part, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts.
Poly (propylene carbonate) is also known as lined polymethyl ethylene carbonate, and it is using carbon dioxide and expoxy propane as Material synthesis
A kind of Wholly-degradable environment-friendly type plastic.In the composite of the present invention, count in parts by weight, poly (propylene carbonate) typical case
But nonrestrictive content is：5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts.
PLA/ Nano titanium nitride master batches refer to mainly by the primary granule of PLA and Nano titanium nitride through being combined.This hair
In bright composite, count in parts by weight, the typical but non-limiting content of PLA/ Nano titanium nitride master batches is：1 part, 2 parts,
3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
Filler can improve processing characteristics, mechanical property, reduction composite cost of composite etc..The present invention's answers
In condensation material, count in parts by weight, the typical but non-limiting content of filler is：3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts,
10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts.
Thermoplastic elastomer (TPE), both possessed the high resiliency of traditional cross-linking vulcanized rubber, ageing-resistant, the every superiority of oil resistivity
Energy；Simultaneously but also with the characteristics of common plasticses are easy to process, processing mode is wide, the processing modes such as injection, extrusion, blowing can be used
Production, its environmentally friendly, nontoxic, comfortable feel, exquisite appearance, product is had more intention, therefore be also more hommization, a Gao Pin
The novel synthetic material of position, and globalization standard environment-friendly materials.In the composite of the present invention, count in parts by weight, heat
The typical but non-limiting content of thermoplastic elastic is：1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5
Part.
Lubricant primarily serves the effect for reducing frictional resistance, is advantageous to the uniform mixing of each raw material, improves composite
Workability.In the composite of the present invention, count in parts by weight, the typical but non-limiting content of lubricant is：0.5
Part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part.
Chain extender is also known as chain extender, be can with the functional group reactionses on linear polymer chain and make strand extension, point
The material of son amount increase, makes each high score subclass raw material rapid polymerization into the bigger polymer of molecular weight, improve resin molecular weight,
Melt viscosity etc., reach the purpose for improving product processing characteristics and mechanical property.In the composite of the present invention, in parts by weight
Meter, the typical but non-limiting content of chain extender are：1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts,
2.6 parts, 2.8 parts or 3 parts.
In the PLA/ Nano titanium nitride master batches of the present invention, count in parts by weight, the typical but non-limiting contents of PLA are：
80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108
Part, 110 parts, 112 parts, 114 parts, 116 parts, 118 parts or 120 parts.
Titanium nitride has typical NaCl types structure, and TiN fusing points are higher than the fusing point of most of transition metal nitrides, and close
Degree is but lower than most metals nitride, therefore is a kind of very distinctive heat proof material.Titanium nitride membrane has well tough
Property and wearability, trapping and anticorrosive property are good, also act as anti-corrosion layer.Nano titanium nitride is that grain diameter is nano level nitrogen
Change titanium, particle is more tiny, and specific surface area is bigger, bigger with the contact area of remaining each raw material, and its feature is than non-nano nitrogen
It is more notable to change titanium.In the PLA/ Nano titanium nitride master batches of the present invention, count in parts by weight, Nano titanium nitride is typical but non-limiting
Content be：0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts or 1.2 parts.
Stabilisers against hydrolysis can avoid PLA hydrolysis, and the melt stability of melt is improved in the process such as extrusion,
Improve the physical and mechanical property of product.In the PLA/ Nano titanium nitride master batches of the present invention, count in parts by weight, resistant to hydrolysis is stable
The typical but non-limiting content of agent is：0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts
Or 1.2 parts.
In the PLA/ Nano titanium nitride master batches of the present invention, count in parts by weight, the typical but non-limiting content of chain extender
For：0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts.
It should be noted that the weight basis all same in the present invention, such as each raw material of the composite of trapping environmental protection
Weight basis is identical with the weight basis of each raw material of PLA/ Nano titanium nitride master batches, is all such as 1 gram.
The composite of above-mentioned trapping environmental protection is prepared using PLA and PLA/ Nano titanium nitride master batches as primary raw material, matches somebody with somebody
Fang Kexue, by the reasonable cooperation of each raw material, given full play to nano-titanium oxide gas barrier advantage and PLA it is degradable excellent
Gesture, not only the feature of environmental protection is good for obtained composite, moreover it is possible to effectively obstructs gas, OTR oxygen transmission rate ratio is compound without Nano titanium nitride
PLA low 8%-25%, while also ensure the machines such as heat endurance and tensile strength and the elongation at break of composite
Tool performance is not suffered a loss, and Product processing is functional.
It is preferably carried out in one kind in mode, the composite is mainly prepared by the raw material of following parts by weight：PLA
30-50 parts, PBAT 24-36 parts, poly (propylene carbonate) 6-18 parts, PLA/ Nano titanium nitride master batch 2-8 parts, filler 5-12 parts, heat
Thermoplastic elastic 2-5 parts, lubricant 0.6-1 parts and chain extender 1.2-2.8 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 84-106 parts, receive
Rice titanium nitride 0.3-1.0 parts, stabilisers against hydrolysis 0.3-1.0 parts and chain extender 0.6-1.4 parts.
It is preferably carried out in one kind in mode, the composite is mainly prepared by the raw material of following parts by weight：PLA
35-45 parts, PBAT 28-32 parts, poly (propylene carbonate) 8-14 parts, PLA/ Nano titanium nitride master batch 3-7 parts, filler 7-10 parts, heat
Thermoplastic elastic 2-4 parts, lubricant 0.6-0.9 parts and chain extender 1.4-2.6 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 88-102 parts, receive
Rice titanium nitride 0.3-0.8 parts, stabilisers against hydrolysis 0.3-0.8 parts and chain extender 0.8-1.2 parts.
It is preferably carried out in one kind in mode, the PLA/ Nano titanium nitrides master batch is mainly by PLA and modified nanometer nitrogen
Change titanium to be prepared, the Nano titanium nitride of the modification is mainly prepared by Nano titanium nitride and silane coupler, the silicon
Alkane coupling agent is the 0.03-3wt.% of the Nano titanium nitride.Nano titanium nitride can be strengthened using modified Nano titanium nitride
With PLA compatibility, and then improve the processing characteristics of composite, improve production efficiency, and further improve composite
The mechanical performance such as tensile strength and elongation at break.
In this preferred embodiment, typical but non-limiting above-mentioned silane coupler is the Nano titanium nitride
0.03wt.%, 0.05wt.%, 0.1wt.%, 0.2wt.%, 0.4wt.%, 0.6wt.%, 0.8wt.%, 1wt.%,
1.2wt.%, 1.4wt.%, 1.6wt.%, 1.8wt.%, 2wt.%, 2.2wt.%, 2.4wt.%, 2.6wt.%,
2.8wt.% or 3wt.%.
It is preferably carried out in one kind in mode, the silane coupler is at least one in KH550, KH560 or KH570
Kind.KH550 is γ-aminopropyl triethoxysilane；KH560 is γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane；
KH570 is γ-methacryloxypropyl trimethoxy silane.Above-mentioned silane coupler is KH550, KH560, KH570,
KH550 and KH560 combination, KH560 and KH570 combination, KH550 and KH570 combination, or, KH550, KH560 and
KH570 combination.
It is preferably carried out in one kind in mode, the thermoplastic elastomer (TPE) is at least one in SBG, POE-g-GMA or MBS
Kind.SBG (Styrene-butadiene epoxide) is epoxy graft phenylethene-butadiene copolymer；POE-g-GMA is second
The graft product of alkene -1- octene copolymers (POE) and GMA (GMA)；MBS(Methacrylate-
Butadiene-Styrene copolymer) it is MBS.Above-mentioned thermoplastic elastomehc
Property body is SBG, POE-g-GMA, MBS, SBG and POE-g-GMA combination, POE-g-GMA and MBS combination, SBG and MBS's
Combination, or, SBG, POE-g-GMA and MBS combination.
Alternatively, the lubricant is erucyl amide and/or EBS.EBS(N,N'-ethylenedi(stearamide))
For ethylene bis stearamide.
Alternatively, the filler is inorganic filler or organic filler.Alternatively, the inorganic filler is silica, cunning
Stone flour, cover at least one of support soil or calcium carbonate.
Second aspect, the invention provides a kind of preparation method of the composite of above-mentioned trapping environmental protection, including following step
Suddenly：
(a) it is granulated and obtains after being well mixed the PLA of formula ratio, Nano titanium nitride, stabilisers against hydrolysis and chain extender
PLA/ Nano titanium nitride master batches；
(b) by PLA/ Nano titanium nitrides master batch, PLA, PBAT, poly (propylene carbonate), filler, the thermoplastic elastic of formula ratio
It is granulated after body, lubricant and chain extender are well mixed and obtains the composite of the trapping environmental protection.
Above-mentioned preparation method technique is simple, easily operated, controllable degree is high, is adapted to produce in enormous quantities, is obtained using this method
To the composite of trapping environmental protection have that the feature of environmental protection is good, gas barrier rate is high, heat endurance is good and the advantages of good mechanical property.
It is preferably carried out in one kind in mode, the Nano titanium nitride first passes around modification, and processing method is：First
The silane coupler of formula ratio and alcohol and water are configured to solution of silane, then by the Nano titanium nitride of formula ratio and the silane
Dried after solution is well mixed.Processing is modified to Nano titanium nitride can strengthen the compatible of Nano titanium nitride and PLA
Property, and then improve the processing characteristics of composite, production efficiency is improved, and further improve the tensile strength of composite and break
Split the mechanical performances such as elongation.Wherein, alcohol and water plays a part of solvent, for dissolving silane coupler.
Alternatively, in above-mentioned solution of silane, count in parts by weight, the content of silane coupler is 15-25 parts, the content of alcohol
For 70-75 parts, the content of water is 5-10 parts.The density and modest viscosity of the solvent of above-mentioned formula.Alternatively, above-mentioned solution of silane
The mode that sprinkling can be selected is sprayed on Nano titanium nitride surface.
It is preferably carried out in one kind in mode, the granulation in step (a) is double-screw extruding pelletizing, and the temperature of twin-screw is
165-175℃；Granulation in step (b) is double-screw extruding pelletizing, and the temperature of twin-screw is 165-180 DEG C.Extruding pelletization has
There is continuity of operation high, mechanically sealed property is good, and impurity is mixed into few, the advantages of yield is high, and labor intensity is small, and noise is small；Above-mentioned step
Suddenly the temperature of (a) and the twin-screw in step (b) is reasonable, if twin-screw temperature is too high, raw material can be bonded at because temperature is too high
In thread groove, convey and move forward with screw rod Effect of Rotation material, extruder production is not normally functioning because under feeding；If
Twin-screw temperature is too low, then raw material can not fully realize melting extrusion.
The temperature of twin-screw is typical but non-limiting in step (a) is：165℃、166℃、167℃、168℃、169
DEG C, 170 DEG C, 171 DEG C, 172 DEG C, 173 DEG C, 174 DEG C or 175 DEG C.The temperature of twin-screw is typical but non-limiting in step (b)
For：165℃、166℃、167℃、168℃、169℃、170℃、171℃、172℃、173℃、174℃、175℃、176℃、
177 DEG C, 178 DEG C, 179 DEG C or 180 DEG C.
The third aspect, the invention provides a kind of composite of above-mentioned trapping environmental protection in plastic foil, polybag, plastic casing
Or the application in plastic bottle.The composite of above-mentioned trapping environmental protection is applied to plastic foil, polybag, plastic casing or plastic bottle
In, above-mentioned plastic product can be made to have that the feature of environmental protection is good, gas barrier rate is high, heat endurance is good and the advantages of good mechanical property.
It should be noted that above-mentioned plastic product can be process using any one method of the prior art, this hair
It is bright that this is not particularly limited.
With reference to embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 1 part of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 1 part of 2- polybutadiene, mustard
1 part of 0.5 part of sour acid amides and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
Embodiment 2
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：35 parts of PLA, PBAT
28 parts, 8 parts of poly (propylene carbonate), 3 parts of PLA/ Nano titanium nitrides master batch, the same l of talcum powder 7 part, 2 parts of 2- polybutadiene, EBS
0.6 part and 1.4 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 88 part, nanometer nitrogen
Change 0.8 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
Embodiment 3
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：45 parts of PLA, PBAT
32 parts, 14 parts of poly (propylene carbonate), 7 parts of PLA/ Nano titanium nitrides master batch, cover support soil 10 parts, 4 parts of TPV, 0.9 part of erucyl amide
With 2.6 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 102 part, nanometer nitrogen
Change 1.2 parts of 0.8 part of titanium, 0.8 part of stabilisers against hydrolysis and chain extender.
Embodiment 4
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
40 parts, 20 parts of poly (propylene carbonate), 10 parts of PLA/ Nano titanium nitrides master batch, 15 parts of calcium carbonate, 5 parts of TPV, erucyl amide and EBS
1 part and 3 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 120 part, nanometer nitrogen
Change 1.5 parts of 1.2 parts of titanium, 1.2 parts of stabilisers against hydrolysis and chain extender.
Embodiment 5
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：40 parts of PLA, PBAT
30 parts, 10 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 8 parts of silica, 3 parts of TPV, 0.8 part of erucyl amide
With 2 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 90 part, nanometer nitrogen
Change 1 part of 0.5 part of titanium, 0.5 part of stabilisers against hydrolysis and chain extender.
Embodiment 6
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 2 parts of 2- polybutadiene, mustard
1.5 parts of 0.5 part of sour acid amides and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 100 part, nanometer nitrogen
Change 1 part of 0.5 part of titanium, 0.5 part of stabilisers against hydrolysis and chain extender.
Embodiment 7
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 2 parts of MBS, 0.5 part of erucyl amide
With 1.5 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 100 part, nanometer nitrogen
Change 1 part of 0.5 part of titanium, 0.5 part of stabilisers against hydrolysis and chain extender.
As different from Example 6, preferably thermoplastic elastomer (TPE)-MBS is employed in the present embodiment.
Embodiment 8
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 2 parts of SBG, 0.5 part of erucyl amide
With 1.5 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 100 part, nanometer nitrogen
Change 1 part of 0.5 part of titanium, 0.5 part of stabilisers against hydrolysis and chain extender.
As different from Example 6, preferably thermoplastic elastomer (TPE)-SBG is employed in the present embodiment.
Embodiment 9
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 2 parts of POE-g-GMA, erucyl amide
0.5 part and 1.5 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 100 part, nanometer nitrogen
Change 1 part of 0.5 part of titanium, 0.5 part of stabilisers against hydrolysis and chain extender.
As different from Example 6, preferably thermoplastic elastomer (TPE)-POE-g-GMA is employed in the present embodiment.
Embodiment 10
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 2 parts of MBS, 0.5 part of erucyl amide
With 1.5 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：It is 100 parts of PLA, modified
1 part of 0.5 part of Nano titanium nitride, 0.5 part of stabilisers against hydrolysis and chain extender；
The Nano titanium nitride of the modification is mainly prepared by Nano titanium nitride and silane coupler DL602, the silicon
Alkane coupling agent DL602 is the 1wt.% of the Nano titanium nitride.
As different from Example 7, modified Nano titanium nitride is employed in the present embodiment.
Embodiment 11
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：60 parts of PLA, PBAT
20 parts, 8 parts of poly (propylene carbonate), 5 parts of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 2 parts of MBS, 0.5 part of erucyl amide
With 1.5 parts of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：It is 100 parts of PLA, modified
1 part of 0.5 part of Nano titanium nitride, 0.5 part of stabilisers against hydrolysis and chain extender；
The Nano titanium nitride of the modification is mainly prepared by Nano titanium nitride and silane coupler KH570, the silicon
Alkane coupling agent KH570 is the 1wt.% of the Nano titanium nitride.
As different from Example 10, preferably silane coupler is employed in the present embodiment.
Embodiment 12
The preparation method of the composite of trapping environmental protection described in embodiment 11, comprises the following steps：
(a) it is granulated and obtains after being well mixed the PLA of formula ratio, Nano titanium nitride, stabilisers against hydrolysis and chain extender
PLA/ Nano titanium nitride master batches；
(b) by the PLA/ Nano titanium nitrides master batch of formula ratio, PLA, PBAT, poly (propylene carbonate), silica, MBS, mustard
It is granulated after sour acid amides and chain extender are well mixed and obtains the composite of the trapping environmental protection.
Embodiment 13
The preparation method of the composite of trapping environmental protection described in embodiment 11, comprises the following steps：
(a) surface modification is carried out to Nano titanium nitride with silane coupler KH570, by the silane coupler of formula ratio
KH570 is configured to solution of silane with alcohol and water, after being then well mixed the Nano titanium nitride of formula ratio and the solution of silane
Drying, in its solution of silane, silane coupler KH570 content is 20 parts by weight, and the content of alcohol is 72 parts by weight, water
Content is 8 parts by weight；
(b) by the PLA of formula ratio, the Nano titanium nitride of modification, stabilisers against hydrolysis and chain extender in homogenizer
After stirring 10min is well mixed, draw ratio is used to obtain PLA/ for 65 double-screw extruding pelletizing (twin-screw temperature is 170 DEG C)
Nano titanium nitride master batch；
(c) PLA/ Nano titanium nitrides master batch, PLA, PBAT, poly (propylene carbonate), silica and the MBS of formula ratio are existed
After being well mixed in low-speed mixer, add the erucyl amide of formula ratio and chain extender stirs 10min in homogenizer and mixed
After closing uniformly, draw ratio is used to obtain the trapping environmental protection for 65 double-screw extruding pelletizing (twin-screw temperature is 175 DEG C)
Composite.
Comparative example 1
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, poly- carbonic acid
Sub- 5 parts of propyl ester, 1 part of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 1 part of 2- polybutadiene, 0.5 part of erucyl amide
With 1 part of chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
As different from Example 1, PBAT has been lacked in the raw material of this comparative example.
Comparative example 2
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), the same l of silica 3 part, 1 part of 2- polybutadiene, 0.5 part of erucyl amide and chain extender 1
Part.
As different from Example 1, PLA/ Nano titanium nitride master batches have been lacked in the raw material of this comparative example.
Comparative example 3
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 1 part of PLA/ Nano titanium nitrides master batch, 3 parts of silica, 0.5 part of erucyl amide and chain extender 1
Part；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
As different from Example 1, same l between having lacked in the raw material of this comparative example, 2- polybutadiene.
Comparative example 4
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 1 part of Nano titanium nitride, the same l of silica 3 part, 1 part of 2- polybutadiene, erucyl amide
0.5 part and 1 part of chain extender.
As different from Example 1, in the raw material of this comparative example, PLA/ Nano titanium nitrides master batch is replaced for nanometer nitrogen
Change titanium.
Comparative example 5
PLA。
Comparative example 6
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：80 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 1 part of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 1 part of 2- polybutadiene, mustard
1 part of 0.5 part of sour acid amides and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
As different from Example 1, the content of the PLA in this comparative example in the raw material of composite is not carried in the present invention
For in the range of.
Comparative example 7
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 12 parts of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 1 part of 2- polybutadiene,
1 part of 0.5 part of erucyl amide and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.3 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
As different from Example 1, PLA/ nano titanium carbide master batches in this comparative example in the raw material of composite contain
Amount is not in scope provided by the present invention.
Comparative example 8
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：20 parts of PLA, PBAT
20 parts, 5 parts of poly (propylene carbonate), 1 part of PLA/ Nano titanium nitrides master batch, the same l of silica 3 part, 1 part of 2- polybutadiene, mustard
1 part of 0.5 part of sour acid amides and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80 part, nanometer nitrogen
Change 0.5 part of 0.1 part of titanium, 0.3 part of stabilisers against hydrolysis and chain extender.
As different from Example 1, Nano titanium nitride in this comparative example in the raw material of PLA/ Nano titanium nitrides master batch
Content is not in scope provided by the present invention.
Comparative example 9
A kind of composite of trapping environmental protection, is mainly prepared by the raw material of following parts by weight：15 parts of PLA, PBAT
45 parts, 22 parts of poly (propylene carbonate), 12 parts of PLA/ Nano titanium nitrides master batch, the same l of silica 2 part, 6 parts of 2- polybutadiene,
5 parts of 1.4 parts of erucyl amide and chain extender；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 50 part, nanometer nitrogen
Change 0.3 part of 0.2 part of titanium, 1.3 parts of stabilisers against hydrolysis and chain extender.
As different from Example 1, the content of all raw materials in this comparative example is not in scope provided by the present invention
It is interior.
Performance test is carried out to the material product in embodiment 1-13 and comparative example 1-9 respectively, as a result as shown in table 1.
The performance test results of table 1
As seen from the above table, embodiment 1-13 oxygen transit dose is below comparative example 1-9, and its tensile strength and fracture are stretched
Long rate is suitable with comparative example 1-9, illustrates the composite of trapping environmental protection provided by the invention and not only has good barrier gas
Effect, and the satisfactory mechanical property of composite, delete any component or change the content of any component or existing PLA
Identical effect can not be realized.
Further analysis shows that embodiment 7-9 combination property is better than embodiment 6, illustrate using preferably thermoplastic elastomehc
Property body can further reduce the oxygen transit dose of composite.The tensile strength and elongation at break of embodiment 10 and 11 are better than
Embodiment 7, illustrate that using modified Nano titanium nitride Nano titanium nitride and PLA compatibility, Jin Erti can be further enhanced
The mechanical performance of high composite.The combination property of the composite for the trapping environmental protection that embodiment 13 is prepared is better than embodiment
11, illustrate that preparation method processing step and technological parameter provided by the invention are reasonable, the synthesis of each raw material can be given full play of
Advantage, the common performance for causing composite are optimal.
Heat stability test is carried out to embodiment 1-13 and comparative example 1-9 material respectively：In the interior that temperature is 60 degree
Placed in environment, it is found that embodiment 1-13 composite flavescence occurs after using 120 days and become fragile；And comparative example 1-9 material
There is flavescence after using 60 days and become fragile in material, and illustrates that the heat endurance of composite provided by the invention is more preferable.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of composite of trapping environmental protection, it is characterised in that be mainly prepared by the raw material of following parts by weight：PLA
20-60 parts, PBAT 20-40 parts, poly (propylene carbonate) 5-20 parts, PLA/ Nano titanium nitride master batch 1-10 parts, filler 3-15 parts,
Thermoplastic elastomer (TPE) 1-5 parts, lubricant 0.5-1 parts and chain extender 1-3 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 80-120 parts, nanometer nitrogen
Change titanium 0.3-1.2 parts, stabilisers against hydrolysis 0.3-1.2 parts and chain extender 0.5-1.5 parts.
2. the composite of trapping environmental protection according to claim 1, it is characterised in that mainly by the raw material of following parts by weight
It is prepared：PLA 30-50 parts, PBAT 24-36 parts, poly (propylene carbonate) 6-18 parts, PLA/ Nano titanium nitride master batch 2-8 parts,
Filler 5-12 parts, thermoplastic elastomer (TPE) 2-5 parts, lubricant 0.6-1 parts and chain extender 1.2-2.8 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 84-106 parts, nanometer nitrogen
Change titanium 0.3-1.0 parts, stabilisers against hydrolysis 0.3-1.0 parts and chain extender 0.6-1.4 parts.
3. the composite of trapping environmental protection according to claim 1, it is characterised in that mainly by the raw material of following parts by weight
It is prepared：PLA 35-45 parts, PBAT 28-32 parts, poly (propylene carbonate) 8-14 parts, PLA/ Nano titanium nitride master batch 3-7 parts,
Filler 7-10 parts, thermoplastic elastomer (TPE) 2-4 parts, lubricant 0.6-0.9 parts and chain extender 1.4-2.6 parts；
The PLA/ Nano titanium nitrides master batch is mainly prepared by the raw material of following parts by weight：PLA 88-102 parts, nanometer nitrogen
Change titanium 0.3-0.8 parts, stabilisers against hydrolysis 0.3-0.8 parts and chain extender 0.8-1.2 parts.
4. the composite of the trapping environmental protection according to claim any one of 1-3, it is characterised in that the PLA/ nanometers nitrogen
Change titanium master batch to be mainly prepared by PLA and modified Nano titanium nitride, the Nano titanium nitride of the modification is mainly by nanometer nitrogen
Change titanium and silane coupler is prepared, the silane coupler is the 0.03-3wt.% of the Nano titanium nitride.
5. the composite of trapping according to claim 4 environmental protection, it is characterised in that the silane coupler be KH550,
At least one of KH560 or KH570.
6. the composite of the trapping environmental protection according to claim any one of 1-3, it is characterised in that the thermoplastic elastic
Body is at least one of SBG, POE-g-GMA or MBS.
7. the preparation method of the composite of the trapping environmental protection described in claim any one of 1-6, it is characterised in that including following
Step：
(a) by the PLA of formula ratio, Nano titanium nitride, stabilisers against hydrolysis and chain extender it is well mixed after be granulated and obtain PLA/ and receive
Rice titanium nitride master batch；
(b) by the PLA/ Nano titanium nitrides master batch of formula ratio, PLA, PBAT, poly (propylene carbonate), filler, thermoplastic elastomer (TPE),
It is granulated after lubricant and chain extender are well mixed and obtains the composite of the trapping environmental protection.
8. the preparation method of the composite of trapping environmental protection according to claim 7, it is characterised in that the nano silicon nitride
Titanium first passes around modification, and processing method is：The silane coupler of formula ratio and alcohol and water are configured to solution of silane first,
Then dried after being well mixed the Nano titanium nitride of formula ratio and the solution of silane.
9. the preparation method of the composite of the trapping environmental protection according to claim 7 or 8, it is characterised in that in step (a)
Granulation be double-screw extruding pelletizing, the temperature of twin-screw is 165-175 DEG C；Granulation in step (b) is made for twin-screw extrusion
Grain, the temperature of twin-screw is 165-180 DEG C.
10. the composite of the trapping environmental protection described in claim any one of 1-6 is in plastic foil, polybag, plastic casing or plastics
Application in bottle.
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