CN110128806A - A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle - Google Patents

A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle Download PDF

Info

Publication number
CN110128806A
CN110128806A CN201910498135.8A CN201910498135A CN110128806A CN 110128806 A CN110128806 A CN 110128806A CN 201910498135 A CN201910498135 A CN 201910498135A CN 110128806 A CN110128806 A CN 110128806A
Authority
CN
China
Prior art keywords
polylactic acid
heat
acid composite
degradation
initiator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910498135.8A
Other languages
Chinese (zh)
Inventor
陈旭升
张宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongshan Perfect Color Resource Co Ltd
Original Assignee
Zhongshan Perfect Color Resource Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongshan Perfect Color Resource Co Ltd filed Critical Zhongshan Perfect Color Resource Co Ltd
Priority to CN201910498135.8A priority Critical patent/CN110128806A/en
Publication of CN110128806A publication Critical patent/CN110128806A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The present invention discloses a kind of lactic acid composite material and preparation method thereof of high degradation rate, it is made of polylactic resin, PBAT resin, inorganic filler, modified starch, organic nucleating agent, coupling agent, chain extender, compounding photoinitiator, thermal-oxidative degradation initiator and food-grade plasticizer, the heat resistance for improving poly-lactic acid material expands the usage scenario of polylactic acid article;Thermal degradation, light degradation and hydrolysis rate after PLA product is discarded are increased, the harsh conditions of industrial compost is avoided the need for, can realize under field conditions (factors) compared to the faster degradation rate of common polylactic acid.The adjuvant used present invention is food-grade raw material, can be applied to food packaging.Equipment used in the preparation method of the lactic acid composite material of high degradation rate provided by the invention is simple, small investment.

Description

A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle
Technical field
The present invention relates to biodegradation material fields, and in particular to a kind of heat-resistance polylactic acid composite material of short degradation cycle And preparation method thereof.
Background technique
In today that environment and sustainable development are the theme, environmentally friendly " green " high molecular material is increasingly by people Favor, PLA (polylactic acid polylactic acid) saves the prominent of petroleum resources etc. because it is reducing environmental pollution It contributes out, has complied with the requirement of sustainable development, while PLA has biodegradable, high-strength and high-modulus, high transparency and good life Many advantages, such as object compatibility, has broad application prospects in sphere of life such as medicine, weaving, agricultural, clothes, becomes research Hot spot.But the disadvantages of its poor heat resistance, crisp property, seriously limits its scope of application.As PLA is unsuitable for requiring to heat resistance Structural material, disposable tableware, coffee cup etc., poor toughness also limit its application on packaging material.Therefore it has to pair PLA is modified to widen its application range.
At present in biodegradation material field, especially there is more in-depth study to polylactic acid mechanism of degradation, still There is presently no the poly-lactic acid products compost and reclaim mechanism of establishing a set of maturation in China, and poly-lactic acid material will not be in common item Effectively degradation is realized under part.
The degradation property of polylactic acid is test to be completed under the conditions of compost, and the requirement of compost condition is more severe at present It carves, if you need to just can achieve biodegradable performance under conditions of 60 DEG C, 80%~90% humidity.
Ideal biodegradable material be refer to it is degradable for CO by microorganism2And H2The material of O is based on standard It is to hold in 20~25 DEG C of natural environment with the biodegradable plastic of test method and the explication of degradation approved Easily it is degraded by microorganisms and releases CO2And H2The material of O.According to this definition, PLA is just not belonging to biodegradable material, Because PLA is not easy to be completely degraded in the natural environment, but from the perspective of compost, PLA is a kind of degradation material, Although degradation in the natural environment is not also studies have shown that PLA can be degraded by multiple-microorganism under control condition appropriate It is very universal because most of natural environment be not able to satisfy compost needed for harsh conditions, because the invention one kind can be with Realize that the PLA material of fast and stable degradation is necessary in most of natural environments.
Photodegradable plastics have a large amount of patent application, but belong on the basis of general nondegradable plastics by increasing light Quick dose is realized, even if common high molecular material adds photosensitizer, but can not also fully achieve degradation, and common high score It will appear a large amount of molecule after sub- material photodissociation, cause the secondary pollution of soil.
Light~biodegradation plastic can also have ignored various initiators in process to the passive shadow of material itself It rings.
Summary of the invention
To overcome defect and blank of the existing technology, the present invention provides a kind of polylactic acid composite wood of high degradation rate Material and preparation method thereof, it is intended to which the degradation condition for reducing polylactic acid achievees the effect that fast degradation, improves product heat resistance, expands The usage scenario of big polylactic acid disposable product;And, small investment simple using equipment.
The present invention proposes a kind of heat-resistance polylactic acid composite material of short degradation cycle, the raw material group including following parts by weight Point:
100 parts of polylactic resin, 10~20 parts of PBAT resin, 15~30 parts of inorganic filler, 1~10 part of modified starch, have 0.1~2.0 part of machine nucleating agent, 0.1~1.0 part of coupling agent, 0.1~0.8 part of chain extender, compound photoinitiator 0.1~1.5 Part, 0.1~1.5 part of thermal-oxidative degradation initiator, 0.1~5.0 part of food-grade plasticizer.
Preferably, the number-average molecular weight Mn of the polylactic acid is 200000-300000, and melt index is in 190 DEG C of x10min Under the conditions of be 15~20g/10min.
Preferably, the thermal-oxidative degradation initiator is cumyl peroxide and benzoyl peroxide 1:1 group in mass ratio At.
Preferably, the organic nucleating agent is two hydrazides of decanedioic acid diphenyl and phenyl-phosphonic acid zinc 1:0.8 in mass ratio Mixture.
Preferably, the compounding photoinitiator presses quality by cationic initiator and transistion metal compound type initiator It compounds and forms than 1:0.5, the cationic initiator is diaryl sulfosalt, triaryl sulfonium salts, one in alkyl sulfosalt Kind or any two kinds of mixture;The transistion metal compound is dibutyl dithiocaarbamate iron and diethyl-dithio The mixture of carbamic acid iron.
Preferably, the chain extender of the preferred model ADR-4468 of the chain extender.
Preferably, the coupling agent selects silane coupling agent KH-560.
Preferably, the inorganic filler is the mixture of one or both of dolomite and glass microballoon, and mesh number is 3500 mesh.
Preferably, the modified starch is one of Acetylated potato starch, carboxymethyl starch, phosphate ester starch or any Two kinds of mixture.
The present invention proposes a kind of preparation method of the heat-resistance polylactic acid composite material of short degradation cycle again, using following weight The raw material of proportion: 100 parts of polylactic resin, 10~20 parts of PBAT resin, 15~30 parts of inorganic filler, modified starch 1~ 10 parts, 0.1~2.0 part of organic nucleating agent, 0.1~1.0 part of coupling agent, 0.1~0.8 part of chain extender, compound photoinitiator 0.1 ~1.5 parts, 0.1~1.5 part of thermal-oxidative degradation initiator, 0.1~5.0 part of food-grade plasticizer is made, and preparation method includes following Step:
(1) polylactic resin, PBAT resin, inorganic filler and modified starch to be dried for use, drying time is 3~5h, Temperature is 80 DEG C;
(2) by modified starch, organic nucleating agent, chain extender, thermal-oxidative degradation initiator, photoinitiator is compounded in mass ratio Example, revolving speed 600r/min uniform in high-speed mixer and mixing, time 5min, temperature control is 60 DEG C, obtains thermal-oxidative degradation and draws It hair agent and compounds photoinitiator and is modified the prodegradant premix that starch sufficiently coats;
(3) polylactic resin, PBAT resin, inorganic filler, coupling agent example in mass ratio are placed in high-speed mixer, are mixed Conjunction stirs evenly, revolving speed 800r/min, time 5min, and temperature control is 80 DEG C, obtains matrix resin premix;
(4) setting double screw extruder temperature is respectively 100~110 DEG C of an area, two 120~130 DEG C of areas, and three areas 170~ 180 DEG C, four 170~180 DEG C of areas, five 175~185 DEG C of areas, six 175~185 DEG C of areas, seven 175~185 DEG C of areas, eight areas 175~ 185 DEG C, 6th area, which are set with, forces side drawing-in device;
(5) matrix resin premix is added to the feeding hopper of double screw extruder, prodegradant premix is placed in pressure In the drawing-in device of side, the extruding pelletization under the process conditions of step (4) setting.
The invention has the benefit that
The lactic acid composite material of high degradation rate of the invention uses polylactic resin, PBAT resin, inorganic filler, changes Property starch, organic nucleating agent, coupling agent, chain extender, compounding photoinitiator, thermal-oxidative degradation initiator and food-grade plasticizer system At.The addition of modified starch can effectively increase the compatibility of PLA resin, and can increase PLA product and be decomposed by the microorganisms Ability, reduce induction period for being decomposed by the microorganisms in the natural environment of PLA product;And modified starch and photoinitiator and Thermal-oxidative degradation agent is used in compounding as certain mass ratio, can be realized the controlled degradation of material.
The introducing of chain extender avoids the degradation of PLA resin in process, guarantees that the mechanical property of material is using It keeps stablizing in the process, while it has also been found that the addition of chain extender can effectively increase product is the shelf life.
Photochemical reaction occurs under light illumination for photoinitiator molecules, generates free radicals compound, then turns to PLA molecule Active hydrogen on chain leads to PLA molecular chain rupture, after induction period, realizes the degradation of PLA.
By realizing and decomposing in the presence of heat and oxygen, the high energy free radical of decomposition product causes for thermal-oxidative degradation agent Other free radical is generated on the free radical of PLA strand, so as to cause the decline of long chain branches degree, reaching makes macromolecular chain Depolymerisation makes molecular weight and molecular weight.
Lactic acid composite material provided by the invention improves the heat resistance of poly-lactic acid material, to expand polylactic acid one The usage scenario of secondary property product;Thermal degradation, light degradation and hydrolysis rate after PLA product is discarded are increased, work is avoided the need for The harsh conditions of industry compost can be realized under field conditions (factors) compared to the faster degradation rate of common polylactic acid.Used in the present invention Auxiliary agent is food-grade raw material, can be applied to food packaging.
Equipment used in the preparation method of the lactic acid composite material of high degradation rate provided by the invention is simple, investment It is few;
Preparation step (1) can be realized the cladding protecting effect to thermal-oxidative degradation initiator and photoinitiator, avoid The adverse reaction that auxiliary agent is likely to occur in screw rod;When can reduce stop of the auxiliary agent in barrel by the operation of auxiliary agent side feed material Between, preventing auxiliary agent from decomposing in mixing shear history causes PLA uncontrollable degradation reaction occur.
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 the heat-resistance polylactic acid composite material of short degradation cycle and preparation method thereof:
A kind of heat-resistance polylactic acid composite material of short degradation cycle, the raw material components including following parts by weight:
100 parts of polylactic resin, 20 parts of PBAT resin, 20 parts of inorganic filler, 5 parts of modified starch, organic nucleating agent 0.5 Part, 0.6 part of coupling agent, 0.4 part of chain extender, 0.3 part of photoinitiator is compounded, 0.3 part of thermal-oxidative degradation initiator, food-grade is plasticized 0.5 part of agent.
Polylactic resin (PLA) preferably manufacturer is NatureWorks LLC company, and the trade mark is the polylactic acid of 3052D, Its number-average molecular weight Mn is 200000-300000, and melt index is 15~20g/10min under the conditions of 190 DEG C of x10min.
Thermal-oxidative degradation initiator is that cumyl peroxide and benzoyl peroxide 1:1 in mass ratio are formed.
Organic nucleating agent is two hydrazides of decanedioic acid diphenyl and the phenyl-phosphonic acid zinc mixture of 1:0.8 in mass ratio.
Photoinitiator is compounded to be compounded by cationic initiator and transistion metal compound type initiator 1:0.5 in mass ratio Composition, cationic initiator are one of diaryl sulfosalt, triaryl sulfonium salts, alkyl sulfosalt or any two kinds mixed Close object;Transistion metal compound is the mixture of dibutyl dithiocaarbamate iron and ferric diethyl dithiocarbamate.
The chain extender that the preferred BASF AG, the U.S. of chain extender is ADR-4468.
Coupling agent selects silane coupling agent KH-560.
Inorganic filler is the mixture of one or both of dolomite and glass microballoon, and mesh number is 3500 mesh.This implementation The preferably mixture of dolomite and glass microballoon is as inorganic filler in example.
Modified starch can be one of Acetylated potato starch, carboxymethyl starch, phosphate ester starch or any two kinds mixed Close object.Preferred Acetylated potato starch in the present embodiment.
The preparation method of the heat-resistance polylactic acid composite material made of above-mentioned raw materials component the following steps are included:
(1) polylactic resin, PBAT resin, inorganic filler and modified starch to be dried for use, drying time is 3~5h, Temperature is 80 DEG C;
(2) by modified starch, organic nucleating agent, chain extender, thermal-oxidative degradation initiator, photoinitiator is compounded in mass ratio Example, revolving speed 600r/min uniform in high-speed mixer and mixing, time 5min, temperature control is 60 DEG C, obtains thermal-oxidative degradation and draws It hair agent and compounds photoinitiator and is modified the prodegradant premix that starch sufficiently coats;
(3) polylactic resin, PBAT resin, inorganic filler, coupling agent example in mass ratio are placed in high-speed mixer, are mixed Conjunction stirs evenly, revolving speed 800r/min, time 5min, and temperature control is 80 DEG C, obtains matrix resin premix;
(4) setting double screw extruder temperature is respectively 100~110 DEG C of an area, two 120~130 DEG C of areas, and three areas 170~ 180 DEG C, four 170~180 DEG C of areas, five 175~185 DEG C of areas, six 175~185 DEG C of areas, seven 175~185 DEG C of areas, eight areas 175~ 185 DEG C, 6th area, which are set with, forces side drawing-in device;
(5) matrix resin premix is added to the feeding hopper of double screw extruder, prodegradant premix is placed in pressure In the drawing-in device of side, the extruding pelletization under the process conditions of step (4) setting.
Carrying out injection molding as raw material using particles of polylactic acid obtained in step (5) can be made into various polylactic acid articles.
The lactic acid composite material of high degradation rate of the invention uses polylactic resin, PBAT resin, inorganic filler, changes Property starch, organic nucleating agent, coupling agent, chain extender, compounding photoinitiator, thermal-oxidative degradation initiator and food-grade plasticizer system At.The present inventor has found that the addition of modified starch can effectively increase the compatibility of PLA resin, and can increase through overtesting The ability for adding PLA product to be decomposed by the microorganisms reduces the induction period that PLA product is decomposed by the microorganisms in the natural environment;And Modified starch and photoinitiator and thermal-oxidative degradation agent being used in compounding in certain mass ratio, can be realized the controllable drop of material Solution.
It should be noted that modified starch and photoinitiator and thermal-oxidative degradation agent are used in compounding, ratio need to reach A certain determining value range, can realize the controlled degradation of material, otherwise will appear material property and decay or can not achieve in advance The purpose degraded in short cycle.
The introducing of chain extender avoids the degradation of PLA resin in process, guarantees that the mechanical property of material is using It keeps stablizing in the process, while by experiment it has also been found that the addition of chain extender can effectively increase the shelf life of product.
Photochemical reaction occurs under light illumination for photoinitiator molecules, generates free radicals compound, then turns to PLA molecule Active hydrogen on chain leads to PLA molecular chain rupture, after induction period, realizes the degradation of PLA.
By realizing and decomposing in the presence of heat and oxygen, the high energy free radical of decomposition product causes for thermal-oxidative degradation agent Other free radical is generated on the free radical of PLA strand, so as to cause the decline of long chain branches degree, reaching makes macromolecular chain Depolymerisation makes molecular weight and molecular weight.
Two hydrazides of decanedioic acid diphenyl can be dissolved into polylactic acid melt at processing temperatures, cooled in resin melt It is crystallized first in journey, and by the intermolecular fibrous crystal for being self-assembly of nanoscale, induction PLA molecule is grown nonparasitically upon another plant knot Crystalline substance, and then reach and accelerate crystallization rate, shorten molding cycle, improve product heat resistance, the purpose of bending modulus and lustrous surface.
Simultaneously we have found that the addition of glass microballoon and dolomite can increase the whiteness and the transparency of material, improve simultaneously Material stiffness keeps product more easily molded, because it is also to influence great factor that the appearance of product is also commercial articles vending in the process.
The effect that cladding can be realized to photoinitiator and thermal-oxidative degradation initiator is added in food-grade plasticizer, into one Step reduces the extent of reaction of the auxiliary agent in barrel.
It should be noted that the purpose that the present invention is reached not merely is being simply mixed for several auxiliary agents, and need to examine Consider the synergistic effect occurred between various auxiliary agents or antagonistic effect.
Lactic acid composite material provided by the invention improves the heat resistance of poly-lactic acid material, to expand polylactic acid one The usage scenario of secondary property product;Thermal degradation, light degradation and hydrolysis rate after PLA product is discarded are increased, work is avoided the need for The harsh conditions of industry compost can be realized under field conditions (factors) compared to the faster degradation rate of common polylactic acid.Used in the present invention Auxiliary agent is food-grade raw material, can be applied to food packaging.
Equipment used in the preparation method of the lactic acid composite material of high degradation rate provided by the invention is simple, investment It is few;The step of preparation method (1), can be realized the cladding protecting effect to thermal-oxidative degradation initiator and photoinitiator, avoid The adverse reaction that auxiliary agent is likely to occur in screw rod;When can reduce stop of the auxiliary agent in barrel by the operation of auxiliary agent side feed material Between, preventing auxiliary agent from decomposing in mixing shear history causes PLA uncontrollable degradation reaction occur.
Experimental data of the invention is as follows:
Lactic acid composite material is made using the raw material of different proportion in the present invention, and gathers made of the raw material by different proportion Lactic acid composite progress outdoor Degrading experiment, eco-toxicity test, heat distortion temperature test, stretches by force compost Degrading experiment Degree test.
The specific data of the raw material of the different proportion of lactic acid composite material are as shown in the table:
Outdoor Degrading experiment condition are as follows: sheet material prepared by material of the present invention (80mm*80mm*2mm) is placed in open air In condition, placement region is Guangdong Province, and outdoor exposure is placed 120 days.
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.
Industrial composting test condition are as follows: sheet material prepared by material of the present invention (80mm*80mm*2mm) is placed in industry In composting conditions (composting conditions are referring to 13432 standard of European Union EN), and quality measurement conservation rate.
Heat distortion temperature, according to ASTM D648 standard testing.
Tensile strength is according to ASTM D638 standard testing.
Stretching strength retentivity measures pure poly-lactic acid material tensile strength, the ratio with the tensile strength of each embodiment, mesh Be to compare the influence for adding various auxiliary agents to material mechanical performance.
Test data is as shown in the table:
According to obtained by above-mentioned test data, the raw material adding proportion in embodiment 2 is best.
Comparative example 1 is not used chain extender and modified starch, leads to photoinitiator, organic peroxide evocating agent is adding Occur to cause mechanical property loss larger, outdoor degradation capability is poor compared with vigorous reaction during work.
Comparative example 2, only adds organic peroxide evocating agent, causes outdoor degradation capability poor, is not added with food-grade increasing Agent is moulded, leads to photoinitiator, organic peroxide evocating agent occurs to cause mechanical property compared with vigorous reaction in process It loses larger.
Comparative example 3, only adds photoinitiator, causes outdoor degradation capability poor.
The processing of side feed material is not used in comparative example 4, preparation method, causes mechanical property loss larger.
There is the protective effect that modified starch is pre-dispersed, this is the notable feature for the scheme that is different from the prior art.
Pre-dispersed protection and be combineding with each other for side feed material can reach effect of the present invention.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations Equivalent structure or equivalent flow shift made by present specification is applied directly or indirectly in other relevant technologies Field is included within the scope of the present invention.

Claims (10)

1. a kind of heat-resistance polylactic acid composite material of short degradation cycle, which is characterized in that the raw material group including following parts by weight Point:
100 parts of polylactic resin, 10-20 parts of PBAT resin, 15~30 parts of inorganic filler, 1~10 part of modified starch, organic nucleation 0.1~2.0 part of agent, 0.1~1.0 part of coupling agent, 0.1~0.8 part of chain extender, 0.1~1.5 part of photoinitiator is compounded, hot oxygen 0.1~1.5 part of initiator, 0.1~5.0 part of food-grade plasticizer of degradation.
2. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the polylactic acid Number-average molecular weight Mn be 200000-300000, melt index under the conditions of 190 DEG C of x10min be 15~20g/10min.
3. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the hot oxygen drop Solving initiator is that cumyl peroxide and benzoyl peroxide 1:1 in mass ratio are formed.
4. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that it is described it is organic at Core agent is two hydrazides of decanedioic acid diphenyl and the phenyl-phosphonic acid zinc mixture of 1:0.8 in mass ratio.
5. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the compounding light Quick initiator by cationic initiator and transistion metal compound type initiator 1:0.5 in mass ratio compounding form, it is described sun from Sub- initiator is one of diaryl sulfosalt, triaryl sulfonium salts, alkyl sulfosalt or any two kinds of mixture;It is described Transistion metal compound is the mixture of dibutyl dithiocaarbamate iron and ferric diethyl dithiocarbamate.
6. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the chain extender It is preferred that the chain extender of model ADR-4468.
7. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the coupling agent Select silane coupling agent KH-560.
8. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that described inorganic to fill out Material is the mixture of one or both of dolomite and glass microballoon, and mesh number is 3500 mesh.
9. the heat-resistance polylactic acid composite material of short degradation cycle according to claim 1, which is characterized in that the modified shallow lake Powder is one of Acetylated potato starch, carboxymethyl starch, phosphate ester starch or any two kinds of mixture.
10. a kind of preparation method of the heat-resistance polylactic acid composite material of short degradation cycle, which is characterized in that use claim 1- Heat-resistance polylactic acid composite material in 9 is raw material, preparation method the following steps are included:
(1) polylactic resin, PBAT resin, inorganic filler and modified starch are dried for use, drying time is 3~5h, temperature It is 80 DEG C;
(2) it by modified starch, organic nucleating agent, chain extender, thermal-oxidative degradation initiator, compounds photoinitiator example in mass ratio and exists High-speed mixer and mixing is uniform, revolving speed 600r/min, time 5min, and temperature control is 60 DEG C, obtains thermal-oxidative degradation initiator It is modified the prodegradant premix that starch sufficiently coats with compounding photoinitiator;
(3) polylactic resin, PBAT resin, inorganic filler, coupling agent are placed in high speed by the mass ratio in claim 1 and mixed It in conjunction machine, is mixed evenly, revolving speed 800r/min, time 5min, temperature control is 80 DEG C, obtains matrix resin premix Material;
(4) setting double screw extruder temperature is respectively 100~110 DEG C of an area, two 120~130 DEG C of areas, three areas 170~180 DEG C, four 170~180 DEG C of areas, five 175~185 DEG C of areas, six 175~185 DEG C of areas, seven 175~185 DEG C of areas, eight areas 175~185 DEG C, 6th area, which are set with, forces side drawing-in device;
(5) matrix resin premix is added to the feeding hopper of double screw extruder, prodegradant premix is placed in pressure side feed Expect in device, the extruding pelletization under the process conditions of step (4) setting.
CN201910498135.8A 2019-06-10 2019-06-10 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle Pending CN110128806A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910498135.8A CN110128806A (en) 2019-06-10 2019-06-10 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910498135.8A CN110128806A (en) 2019-06-10 2019-06-10 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle

Publications (1)

Publication Number Publication Date
CN110128806A true CN110128806A (en) 2019-08-16

Family

ID=67580946

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910498135.8A Pending CN110128806A (en) 2019-06-10 2019-06-10 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle

Country Status (1)

Country Link
CN (1) CN110128806A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964298A (en) * 2019-12-20 2020-04-07 深圳市祥鸿辉科技有限公司 Biodegradable modified material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602884A (en) * 2009-06-25 2009-12-16 浙江海正生物材料股份有限公司 A kind of heat-resistance polylactic acid composite material and preparation method thereof
CN101805499A (en) * 2010-03-15 2010-08-18 任伟 Full-degradable thermoplastic composite material and sheet thereof
CN102702704A (en) * 2012-06-19 2012-10-03 张家港柴能生物科技有限公司 Degradable polylactic acid (PLA) composite material and preparation method thereof
CN102863654A (en) * 2012-10-11 2013-01-09 武汉华丽环保科技有限公司 Starch and polylactic acid composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602884A (en) * 2009-06-25 2009-12-16 浙江海正生物材料股份有限公司 A kind of heat-resistance polylactic acid composite material and preparation method thereof
CN101805499A (en) * 2010-03-15 2010-08-18 任伟 Full-degradable thermoplastic composite material and sheet thereof
CN102702704A (en) * 2012-06-19 2012-10-03 张家港柴能生物科技有限公司 Degradable polylactic acid (PLA) composite material and preparation method thereof
CN102863654A (en) * 2012-10-11 2013-01-09 武汉华丽环保科技有限公司 Starch and polylactic acid composite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
丁浩: "《塑料应用技术》", 30 January 1999, 化学工业出版社 *
徐鼐: "《通用级聚乳酸的改性与加工成型》", 30 January 2016, 中国科学技术大学出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964298A (en) * 2019-12-20 2020-04-07 深圳市祥鸿辉科技有限公司 Biodegradable modified material and preparation method thereof

Similar Documents

Publication Publication Date Title
TW593514B (en) Starch-based fully-biodegradable material and its preparation method
US20080153940A1 (en) Biodegradable compositions and biodegradable articles made thereof
EP2586821B1 (en) Degradable starch-based plastic masterbatch and preparation method thereof
CN101544813B (en) Rapid crystallization polylactic acid composite material and preparation method thereof
CN101205356A (en) Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid
Ren et al. Study on biodegradable starch/OMMT nanocomposites for packaging applications
CN106221165B (en) A kind of whole life cycle design of high-barrier and preparation method thereof
JP2006328117A (en) Impact-resistant environmental material, method for producing the same, and molded article
CN101475735A (en) Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy
CN108047658B (en) Biodegradable polyester agricultural mulching film
CN102653601A (en) Preparation method of completely biodegradable plastic resin and film products thereof
CN105838047A (en) Biodegradable modified lignin particles and production method thereof
CN103087484A (en) Biodegradable composite film material of controllable degradation rate and preparation method thereof
CN106336531A (en) Modified corn straw granule enhanced PBAT [poly(butyleneadipate-co-terephthalate)] starch composite material and preparation method thereof
CN104387732A (en) Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof
CN110128806A (en) A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle
CN109627709B (en) Degradable bio-based master batch and preparation method and application thereof
CN102153844A (en) High-impact heat-resisting polylactic resin with high light transmittance and preparation method of high-impact heat-resisting polylactic resin
CN103788603B (en) A kind of poly(lactic acid) two-way stretch frosted film and preparation method thereof
CN108219406A (en) A kind of flame retardant type Based Full-degradable Plastics Film and preparation method thereof
CN112048162A (en) Full-biodegradable modified plastic for plastic-uptake thin-wall products and preparation method thereof
KR20070119304A (en) Biodegradable composition including cellulose derivative
US20120302671A1 (en) Compositions comprising polylactic acid, bentonite, and gum arabic
CN108641318B (en) Biodegradable polyhydroxycarboxylic acid alloy material and preparation method thereof
US20130131225A1 (en) Compositions comprising polylactic acid and gum arabic

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination