CN106633722A - Anti-tearing biodegradable material with high toughness and preparation method of anti-tearing biodegradable material - Google Patents
Anti-tearing biodegradable material with high toughness and preparation method of anti-tearing biodegradable material Download PDFInfo
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- CN106633722A CN106633722A CN201611028759.6A CN201611028759A CN106633722A CN 106633722 A CN106633722 A CN 106633722A CN 201611028759 A CN201611028759 A CN 201611028759A CN 106633722 A CN106633722 A CN 106633722A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention discloses an anti-tearing biodegradable material with high toughness. The anti-tearing biodegradable material is prepared from the following substances in percentage by mass: 30%-96.3% of PLA (polylactic acid), 5%-60% of PBAT (poly (butyleneadipate-co-terephthalate)), 1%-30% of a plasticizer, 0.5%-15% of a nano-material, 0-20% of mineral powder, 0.1%-0.5% of an epoxy chain extender, 0.1%-2% of a coupling agent and 0.1%-1% of an antioxidant. The biodegradable material is prepared with a two-step melt blending process: (1) the nano-material is subjected to surface treatment by a high-speed mixer, and then a primary material of the PBAT/nano-material is prepared by a high-speed and high-torque twin-screw extruder; (2) reaction plasticization is completed by the twin-screw extruder in the front section of the extruder with a step-by-step feeding method, and reactive chain extension and capacity increasing are realized in the rear section. The material has the advantages of high tear strength and good flexibility, and has good application prospect in express, food, clothing, daily necessity packaging and other fields.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of tear-proof high tenacious biodegradable material and
Its preparation method, and in particular to a kind of nano-material modified, acetyl epoxidised vegetable oleic acid adipic acid glyceride plasticising toughness reinforcing
Biodegradable material and preparation method thereof.The material has the advantages that tear-proof and high tenacity.
Background technology
In recent years, net purchase has become a kind of important shopping way.National express delivery amount reaches 20,600,000,000 within 2015,
Increase by 48% on a year-on-year basis, consume woven bag 29.6 hundred million, polybag 82.6 hundred million, packing case 9,900,000,000,169.5 hundred million meters of adhesive tape, CO2
Discharge 23,000,000 tons.
It is presently used for express delivery and is packaged with poly-bag, file envelope, bubble bags and woven bag etc..The express delivery that polyethylene (PE) makes
The advantages of poly-bag low cost, good easy to use and water resistance, be the main material of express delivery packaging.However, due to polyethylene without
Method degraded, cost recovery are high, resulting express delivery packaging waste broad covered area, big to environmental hazard.
In June, 2016, green hand's network takes 32 global logistics affiliates and starts " green dynamic plan ", and promise is replaced to the year two thousand twenty
The packaging material for changing 50% are 100% degradable green packaging material.Biodegradable material shows good in fields such as express delivery packagings
Good application prospect, be solve packaging waste pollution, one of the effective means that reduces discharging with carbon drop of preserving our planet.
At present, the species of Biodegradable material has PLA (PLA), polyadipate/butylene terephthalate
(PBAT), polycaprolactone (PCL) and polyhydroxyalkanoate (PHA) etc..Wherein, PLA is that a kind of price is low, forms sediment from plant
Powder, can truly realize biodegradation material completely capable of circulation.The tensile strength of PLA is high, transparency is good and printing
Can be excellent, but poor toughness, tearing strength are low, it is impossible to meet the requirement of express delivery packaging.PBAT pliabilities are good, elongation at break
Height, but its tensile strength is low, tearing strength is poor, price is higher, is directly used in express delivery packaging cost performance undesirable.
By PLA/PBAT blending and modifyings, obtain that tear-proof is good, high-ductility by plasticising, increase-volume, toughness reinforcing and nanometer anchorage technology
High and moderate Biodegradable material, in necks such as express delivery packaging, commodity packaging, medical supplies packaging and packagings for foodstuff
Domain is with a wide range of applications.
The content of the invention
The primary and foremost purpose of the present invention is to overcome shortcoming present in above-mentioned prior art with deficiency, there is provided a kind of tear-proof
High tenacious biodegradable material.The present invention adds nano material, coupling agent, plasticizer and epoxy with PLA/PBAT as base material
The components such as chain extender, are prepared using two-step method melt blending technique.
Another object of the present invention is to provide the preparation method of described tear-proof high tenacious biodegradable material.
The purpose of the present invention is achieved through the following technical solutions：A kind of tear-proof high tenacious biodegradable material, by such as
Under material composition by mass percentage：30%～96.3%PLA, 5%～60%PBAT, 1%～30% plasticizer,
0.5%～15% nano material, 0～20% mineral powder, 0.1～0.5% epoxy chain extenders, 0.1～2% coupling agent and
0.1%～1% antioxidant.
Described PLA is the PLA that number-average molecular weight is 50000～200000, preferred number average molecular weight is 80000～
120000 PLA.
Described PBAT is polyadipate/butylene terephthalate that number-average molecular weight is 30000～120000, preferably
For polyadipate/butylene terephthalate that number-average molecular weight is 50000～100000.
Described plasticizer is acetyl epoxidized fatty acid ester, preferably acetyl epoxidised vegetable oleic acid adipic acid glyceride
Oligomer.
The structure of described acetyl epoxidised vegetable oleic acid adipic acid glycerine ester oligomer is as follows:
Wherein, m=6～8, n=8～6, k=3～4, molecular weight is 2000～3000.
Described nano material is one or more in the nano silicon of a diameter of 0.1～20nm, CNT
Mixture.
Described mineral powder is one kind or at least two mixture in calcium carbonate, talcum powder, barium sulfate.
Described epoxy chain extenders be acrylate, GMA and cinnamic copolymer, its ring
Oxygen equivalent is 6～8.
Described coupling agent is the siloxanes containing epoxide group, preferably glycidyl ether oxygen propyl trimethoxy silicon
Alkane.
Described antioxidant for plastic processing antioxidant, preferably phenolic antioxidant.
Described phenolic antioxidant is preferably four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters
Or/and β-positive octadecanol ester (1076) of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid (1010).
Described tear-proof, the Biodegradable material of high tenacity can adopt Single screw extrusion technique, banburying process or double
Screw Extrusion technique is prepared.
Preferably, described tear-proof, the Biodegradable material of high tenacity are prepared using two-step method melting mixing method,
Comprise the steps：
(1) surface treatment of nano material and high shear melting mixing disperse
First, nano material is surface-treated using high-speed mixer, then, using high rotating speed, the double spiral shells of high torque
Bar extrusion mechanism realizes the high dispersive of nano material for the step material of PBAT/ nano materials one；
(2) prepared by PLA/PBAT proprietary materials
Using big L/D ratio (L/D >=48:1) double screw extruder, realized in extruder by the method for Multistep feeding
Leading portion completes to react plasticising, and in posterior segment reactive chain extension and increase-volume are realized.
The present invention has the following advantages and effect relative to prior art：
(1) after being pre-processed to nanosized SiO_2 or carbon nano tube surface using glycidyl ether oxygen propyl trimethoxy silicane again
It is bonded with PBAT melt blendings, its methoxy hydrolysis and with silica or CNT, its epoxy radicals and PBAT end groups are reacted,
Realize that nanoscale disperses by high shear and increasing reaction, produce anchoring effect, improve tearing strength；
(2) acetyl epoxidised vegetable oleic acid adipic acid glyceride is adopted for plasticizer, using its epoxy radicals and the end group of PLA
Generation chemical reaction, realizes reactive plasticising, overcomes the difficult problem that plasticizer is easily separated out and consumption cannot be improved, and obtains good
Plasticising, toughening effect.
Description of the drawings
Fig. 1 is the flow chart of the surface treatment of the nano material of embodiment 1；
Fig. 2 is the flow chart for preparing the step material of PBAT/ nano materials one of embodiment 1；
Fig. 3 is the preparation flow figure of the tear-proof high tenacious biodegradable material of embodiment 1.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
In following embodiment, described PLA 4060D, PLA101 respectively purchased from Natrueworks companies of the U.S. and
Zhejiang Hai Zheng companies；PBAT TH801 are purchased from Tun He companies of Xinjiang Lanshan County；Acetyl epoxidised vegetable oleic acid adipic acid glyceride is
Guangzhou Hai Erma vegetable fat Co., Ltd provides；Nano silicon can chemical industry HN-200 purchased from sky；CNT CNTS-5
(average caliber 5nm) and CNTS-10 (average caliber 10nm) are purchased from Shenzhen Sanshun Zhongke New Material Co., Ltd.；It is silane coupled
Agent KH-560 is purchased from Nanjing chemical company forward；The epoxy chain extenders trade mark is 4370, purchased from Shanxi chemical research institute, other raw materials
And reagent etc., if no special instructions, it is the raw material and reagent that can be obtained from commercial sources such as conventional markets.
Embodiment 1
The nano silicon HN-200 of 98kg is accurately weighed, using high-speed mixer 80 DEG C are heated to, mixed at high speed is simultaneously
With the KH-560 that spray pattern adds 2kg, mix 20 minutes, the Nano-meter SiO_2 of surface treatment is obtained2。
The nanosized SiO_2 of the above-mentioned surface treated of 20kg and the PBAT TH801 of 80kg are accurately weighed, then using major diameter
Than for 40：1 double screw extruder carries out melting mixing, and extrusion temperature is 160～170 DEG C, and screw speed 800rpm is obtained
PBAT/SiO2One step material.
Accurately weigh the PBAT/SiO of PLA 4060D, 75kg of 10kg2The acetyl epoxidized vegetable oil of one step material, 10kg
Sour adipic acid glyceride, the calcium carbonate of 4.7kg, the antioxidant 1010 of the epoxy chain extenders 4370,0.1kg of 0.2kg.By above-mentioned group
Point be pre-mixed it is uniform, using double screw extruder melting mixing, the thermal treatment zone of extruder from the temperature of feed opening to head according to
It is secondary to be set as：130 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 300rpm, tear-proof high tenacity is obtained can
Degradable material.
Embodiment 2
The HN-200 of 95kg is accurately weighed, using high-speed mixer 80 DEG C are heated to, mixed at high speed is simultaneously added with spray pattern
Plus the KH-560 of 5kg, mix 20 minutes, the Nano-meter SiO_2 of surface treatment is obtained2。
Accurately weigh the Nano-meter SiO_2 of the above-mentioned surface treated of 10kg2With the PBAT TH801 of 90kg, then using major diameter
Than for 40：1 double screw extruder carries out melting mixing, and extrusion temperature is 160～170 DEG C, and screw speed 800rpm is obtained
PBAT/SiO2One step material.
Accurately weigh the PBAT/SiO of PLA 4060D, 30kg of 40kg2The acetyl epoxidized vegetable oil of one step material, 15kg
Sour adipic acid glyceride, the talcum powder of 14.8kg, the antioxidant 1076 of the epoxy chain extenders 4370,0.1kg of 0.1kg.Will be above-mentioned
Component is pre-mixed uniformly, using double screw extruder melting mixing, the temperature of the thermal treatment zone of extruder from feed opening to head
It is set as successively：130 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 200rpm is obtained tear-proof high tenacity
Degradation material.
Embodiment 3
The surface treatment of nano silicon and PBAT/SiO2One step preparation method for material is with embodiment 2.
Accurately weigh the PBAT/SiO of PLA 4060D, 19.3kg of 50kg2The acetyl epoxidised vegetable of one step material, 30kg
The antioxidant 1076 of oleic acid adipic acid glyceride, the epoxy chain extenders 4370,0.2kg of 0.5kg.Said components are pre-mixed
Even, using double screw extruder melting mixing, the thermal treatment zone of extruder is set as successively from the temperature of feed opening to head：130
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 500rpm is obtained tear-proof high-toughness degradable material.
Embodiment 4
The surface treatment of nano silicon and PBAT/SiO2One step preparation method for material is with embodiment 2.
Accurately weigh the PBAT/SiO of the PLA 101,20kg of 75kg2The acetyl epoxidised vegetable oleic acid of one step material, 4.5kg
The antioxidant 1076 of adipic acid glyceride, the epoxy chain extenders 4370,0.2kg of 0.3kg.Said components are pre-mixed uniformly,
Using double screw extruder melting mixing, the thermal treatment zone of extruder is set as successively from the temperature of feed opening to head：130℃、
180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 500rpm is obtained tear-proof high-toughness degradable material.
Embodiment 5
The surface treatment of nano silicon and PBAT/SiO2One step preparation method for material is with embodiment 2.
Accurately weigh the PBAT/SiO of the PLA 101,5.5kg of 90kg2The acetyl epoxidised vegetable oleic acid of one step material, 4kg
The antioxidant 1076 of adipic acid glyceride, the epoxy chain extenders 4370,0.2kg of 0.3kg.Said components are pre-mixed uniformly,
Using double screw extruder melting mixing, the thermal treatment zone of extruder is set as successively from the temperature of feed opening to head：130℃、
180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 500rpm is obtained tear-proof high-toughness degradable material.
Embodiment 6
The CNT CNTS-5 of 95kg is accurately weighed, using high-speed mixer 80 DEG C are heated to, mixed at high speed and to spray
Mist mode adds the KH-560 of 5kg, mixes 20 minutes, and the carbon nano tube CNTS-5 of surface treatment is obtained.
Nano-sized carbon CNTS-5 of the above-mentioned surface treated of 10kg and the PBAT TH801 of 90kg are accurately weighed, using banburying
Machine is kneaded 10 minutes under conditions of being 40rpm in 160 DEG C, rotating speed, then adopts draw ratio for 40：1 single screw extrusion machine enters
Row melting mixing, extrusion temperature is 160～170 DEG C, and screw speed 800rpm is obtained the step material of PBAT/CNTS-5 mono-.
Accurately weigh the step material of PBAT/CNTS-5 mono-, the acetyl epoxidized vegetable oil of 15kg of the PLA 101,30kg of 40kg
Sour adipic acid glyceride, the talcum powder of 14.4kg, the antioxidant 1076 of the epoxy chain extenders 4370,0.5kg of 0.1kg.Will be above-mentioned
Component is pre-mixed uniformly, using double screw extruder melting mixing, the temperature of the thermal treatment zone of extruder from feed opening to head
It is set as successively：130 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 200rpm is obtained tear-proof high tenacity
Degradation material.
Embodiment 7
Nano silicon, the CNT CNTS-10 of 45kg of 50kg are accurately weighed, is heated to using high-speed mixer
80 DEG C, mixed at high speed and with spray pattern add 5kg KH-560, mix 20 minutes, be obtained surface treatment nano material mix
Compound.
The nano material mixture of the above-mentioned surface treated of 10kg and the PBAT TH801 of 90kg are accurately weighed, is then adopted
It is 40 with draw ratio：1 double screw extruder carries out melting mixing, and extrusion temperature is 160～170 DEG C, screw speed 800rpm,
The prepared step material of PBAT/ nano materials mixture one.
Accurately weigh the step material of PBAT/ nano materials mixture one of PLA, 30kg of 40kg, the acetyl epoxidation of 15kg to plant
Thing oleic acid adipic acid glyceride, the barium sulfate of 13.9kg, the antioxidant 1076 of the epoxy chain extenders 4370,1kg of 0.1kg.Will be upper
State component to be pre-mixed uniformly, using double screw extruder melting mixing, the temperature of the thermal treatment zone of extruder from feed opening to head
Degree is set as successively：130 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 200rpm is obtained tear-proof high-ductility
Property degradation material.
Reference examples 1
Accurately weigh PBAT, 15kg of PLA, 30kg of 40kg acetyl epoxidised vegetable oleic acid adipic acid glyceride,
The antioxidant 1010 of the talcum powder of 14.8kg, the epoxy chain extenders 4370,0.1kg of 0.1kg.Said components are pre-mixed
Even, using double screw extruder melting mixing, the thermal treatment zone of extruder is set as successively from the temperature of feed opening to head：130
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 200rpm is obtained tear-proof high-toughness degradable material.
Reference examples 2
PBAT/SiO2The preparation method of one step material is with embodiment 1.
Accurately weigh the PBAT/SiO of PLA, 24.5kg of 75kg2The epoxy chain extenders 4370,0.2kg of one step material, 0.3kg
Antioxidant 1076.Said components are pre-mixed uniformly, using double screw extruder melting mixing, the thermal treatment zone of extruder from
The temperature of feed opening to head is set as successively：130 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, rotating speed 500rpm,
Tear-proof high-toughness degradable material is obtained.
Reference examples 3
The preparation method of the step material of PBAT/CNTS-5 mono- is with embodiment 6.
Accurately weigh the step material of PBAT/CNTS-5 mono-, the barium sulfate of 13.9kg, the epoxy of 0.1kg of PLA, 30kg of 40kg
The antioxidant 1076 of chain extender 4370,1kg.Said components are pre-mixed uniformly, using double screw extruder melting mixing, are squeezed
The thermal treatment zone for going out machine is set as successively from the temperature of feed opening to head：130℃、180℃、180℃、180℃、180℃、180
DEG C, rotating speed 200rpm is obtained tear-proof high-toughness degradable material.
Reference examples 4
The preparation method of PBAT/ nano material mixtures is with embodiment 7.
Accurately weigh PBAT/ nano material mixtures, the talcum powder of 14.4kg, the ring of 0.1kg of PLA, 45kg of 40kg
The antioxidant 1010 of oxygen chain extender 4370,0.5kg.Said components are pre-mixed uniformly, it is mixed using double screw extruder melting
Refining, the thermal treatment zone of extruder is set as successively from the temperature of feed opening to head：130℃、180℃、180℃、180℃、180
DEG C, 180 DEG C, rotating speed 200rpm is obtained tear-proof high-toughness degradable material.
Embodiment effect
Embodiment 1～7 and reference examples 1～4 are prepared into tear-proof high tenacious biodegradable material carries out performance survey
Examination, method of testing is as follows, and test result is shown in Table 1.
Melt index is tested according to GB 3682-2000,190 DEG C of temperature, load 2.16Kg.
Tensile strength and elongation at break press GB/T 1040.3-2006 tests, and rate of extension is 200mm/min.
Tearing strength is carried out according to method described in GB/T 16578-1996.
The embodiment the performance test results of table 1
The embodiment the performance test results of table 2
The reference examples the performance test results of table 3
Knowable to embodiment 1-7, as plasticizer loading increases, the elongation at break increase of material, toughness is improved；With
Nano-meter SiO_22Or content of carbon nanotubes increases, the tearing strength increase of material；Add nano material simultaneously and acetyl epoxidation is planted
Thing oleic acid adipic acid glyceride can prepare the good Biodegradable material of elongation at break height, tearing strength, its melt flows speed
Rate is of a relatively high.And in comparative example, due to without adding above two component simultaneously, the tearing strength of material is poor, fracture is stretched
Long rate is low, melt flow rate (MFR) is less.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of tear-proof high tenacious biodegradable material, it is characterised in that by material group as follows by mass percentage
Into：30%～96.3%PLA, 5%～60%PBAT, 1%～30% plasticizer, 0.5%～15% nano material, 0～20%
Mineral powder, 0.1～0.5% epoxy chain extenders, 0.1～2% coupling agent and 0.1%～1% antioxidant.
2. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described PLA is number
Average molecular weight is 50000～200000 PLA.
3. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described PBAT is number
Average molecular weight is 30000～120000 polyadipate/butylene terephthalate.
4. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described plasticizer is
Acetyl epoxidised vegetable oleic acid adipic acid glycerine ester oligomer.
5. tear-proof high tenacious biodegradable material according to claim 4, it is characterised in that described acetyl epoxy
The structure for changing vegetable oil acid adipic acid glycerine ester oligomer is as follows:
Wherein, m=6～8, n=8～6, k=3～4, molecular weight is 2000～3000.
6. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described nano material
For the mixture of one or more in the nano silicon of a diameter of 0.1～20nm, CNT.
7. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described mineral powder
For the one kind in calcium carbonate, talcum powder, barium sulfate or at least two mixture；
Described epoxy chain extenders are acrylate, GMA and cinnamic copolymer, and its epoxy is worked as
Measure as 6～8；
Described coupling agent is the siloxanes containing epoxide group.
8. tear-proof high tenacious biodegradable material according to claim 1, it is characterised in that described antioxidant is
Phenolic antioxidant.
9. tear-proof high tenacious biodegradable material according to claim 8, it is characterised in that described phenols antioxygen
Agent is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters or/and β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) the positive octadecanol ester of propionic acid.
10. tear-proof described in claim 1, the Biodegradable material of high tenacity adopt two-step method melting mixing method system
It is standby, comprise the steps：
(1) surface treatment of nano material and high shear melting mixing disperse
First, nano material is surface-treated using high-speed mixer, then, is squeezed using high rotating speed, high torque twin-screw
Go out machine and prepare the step material of PBAT/ nano materials one, realize the high dispersive of nano material；
(2) prepared by PLA/PBAT proprietary materials
Using big L/D ratio (L/D >=48:1) double screw extruder, the leading portion in extruder is realized by the method for Multistep feeding
Complete to react plasticising, in posterior segment reactive chain extension and increase-volume are realized.
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| CN113045879A (en) * | 2021-03-16 | 2021-06-29 | 漯河市瑞博塑胶有限公司 | High-tear-resistance PLA-PBAT composite degradable resin and preparation method and application thereof |
| CN114269862A (en) * | 2019-06-13 | 2022-04-01 | 斯瓦蒙卢森堡公司 | Degradable extruded webs made from polymer blend compositions |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724950A (en) * | 2013-12-26 | 2014-04-16 | 安徽聚美生物科技有限公司 | Composition containing PBAT (polybutyrate adipate terephthalate) and preparation method thereof as well as PBAT preservative film |
| CN104479304A (en) * | 2014-12-10 | 2015-04-01 | 金发科技股份有限公司 | Full-biodegradable composite as well as preparation method and application of full-biodegradable composite |
| CN105623214A (en) * | 2016-01-13 | 2016-06-01 | 广州市海珥玛植物油脂有限公司 | Plasticized biodegradable polyester film and preparation method thereof |
-
2016
- 2016-11-21 CN CN201611028759.6A patent/CN106633722B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724950A (en) * | 2013-12-26 | 2014-04-16 | 安徽聚美生物科技有限公司 | Composition containing PBAT (polybutyrate adipate terephthalate) and preparation method thereof as well as PBAT preservative film |
| CN104479304A (en) * | 2014-12-10 | 2015-04-01 | 金发科技股份有限公司 | Full-biodegradable composite as well as preparation method and application of full-biodegradable composite |
| CN105623214A (en) * | 2016-01-13 | 2016-06-01 | 广州市海珥玛植物油脂有限公司 | Plasticized biodegradable polyester film and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| S.W.KO等: "Morphological and rheological characterization of multi-walled carbon nanotube/PLA/PBAT blend nanocomposites", 《POLYM. BULL.》 * |
| 丁永涛等: "《高分子复合材料研究新进展》", 31 December 2005, 黄河水利出版社 * |
| 周文英等: "《导热高分子材料》", 30 April 2014, 国防工业出版社 * |
| 徐鼐: "《通用级聚乳酸的改性与加工成型》", 31 January 2016, 中国科学技术大学出版社 * |
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| CN108047667A (en) * | 2017-12-06 | 2018-05-18 | 海南大学 | A kind of polylactic acid/castor oil blend and preparation method thereof |
| CN109401227A (en) * | 2018-10-25 | 2019-03-01 | 南京五瑞生物降解新材料研究院有限公司 | Using the PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation |
| CN109535470B (en) * | 2018-11-21 | 2021-04-13 | 朱志荣 | High-efficiency preparation method of high-strength high-toughness degradable polyester polymer |
| CN109535470A (en) * | 2018-11-21 | 2019-03-29 | 朱志荣 | A kind of high efficiency preparation method of high-intensity and high-tenacity degradable poly esters polymer |
| CN114269862A (en) * | 2019-06-13 | 2022-04-01 | 斯瓦蒙卢森堡公司 | Degradable extruded webs made from polymer blend compositions |
| CN110583326A (en) * | 2019-09-30 | 2019-12-20 | 苏州中达航材料科技有限公司 | Three-layer co-extrusion fully-degradable mulching film and production process thereof |
| CN110583326B (en) * | 2019-09-30 | 2021-04-23 | 苏州中达航材料科技有限公司 | Three-layer co-extrusion fully-degradable mulching film and production process thereof |
| CN111621239A (en) * | 2020-05-16 | 2020-09-04 | 中国科学院理化技术研究所 | Full-biodegradable adhesive tape and preparation method thereof |
| CN111993741A (en) * | 2020-09-11 | 2020-11-27 | 中国科学院长春应用化学研究所 | Paper-plastic composite material and preparation method thereof |
| CN111993741B (en) * | 2020-09-11 | 2022-02-22 | 中国科学院长春应用化学研究所 | Paper-plastic composite material and preparation method thereof |
| CN112778721A (en) * | 2020-12-30 | 2021-05-11 | 福建恒安集团有限公司 | Preparation method of high-toughness hydrolysis-resistant PLA material and packaging box |
| CN113045879A (en) * | 2021-03-16 | 2021-06-29 | 漯河市瑞博塑胶有限公司 | High-tear-resistance PLA-PBAT composite degradable resin and preparation method and application thereof |
| CN114854185A (en) * | 2022-07-06 | 2022-08-05 | 雄县立亚包装材料有限公司 | Biodegradable polymer composite material and preparation method thereof |
| CN114854185B (en) * | 2022-07-06 | 2022-11-22 | 雄县立亚包装材料有限公司 | Biodegradable polymer composite material and preparation method thereof |
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