CN107118309A - A kind of biodegradable polyesters alloy and preparation method thereof - Google Patents
A kind of biodegradable polyesters alloy and preparation method thereof Download PDFInfo
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- CN107118309A CN107118309A CN201710491615.2A CN201710491615A CN107118309A CN 107118309 A CN107118309 A CN 107118309A CN 201710491615 A CN201710491615 A CN 201710491615A CN 107118309 A CN107118309 A CN 107118309A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Two kinds and the compound method for preparing alloy of above biodegradable polyesters are realized the present invention relates to a kind of easy economy.The present invention is based on reactive extrusion technology, fed using one-step method, directly difunctional small molecule and initiator are mixed into biodegradable polyesters component, the polymerization and the reaction of epoxide group and polyester molecule of vinyl are realized in twin screw extrusion, realize chain extension with it is compatible.The biodegradable polyesters alloy, includes the component composition of following parts by weight：100 parts of biodegradable polyesters, 0.05 1.5 parts of bulking agent component A, 0.05 2.5 parts of bulking agent component B, 0.01 0.05 parts of initiator, 03 parts of lubricant, 0 40 parts of filler.Polyester alloy provided by the present invention has performance adjustable, product fully biodegradable, and small molecule noresidue can be applied to the multiple fields such as film, wire rod, sheet material.
Description
Technical field
Belong to technical field of novel materials the present invention relates to one kind, specifically relate to a kind of easy economy and realize two kinds and above life
The compound method for preparing alloy of Biodegradable polyester.
Background technology
Using oil such as polyethylene, polypropylene, polyvinyl chloride, polystyrene as the common resins of raw material, due to its quality
Gently, the excellent feature of machined, performance and be widely used in the various fields such as commodity, packaging material, household appliances.But,
These naval stores after use, good persistence are still shown in abandonment stage, are not gone out within considerable time
Now degrade, the ecosystem is brought and had a strong impact on.Particularly substantial amounts of disposable high molecular products are abandoned, and cause " white dirt
Environmental crisis as dye ".
In order to solve this problem, a variety of polyester resin with thermoplasticity and with biodegradability are developed, existing
Just there is a PLA (PLA) have been carried out large-scale production, polycaprolactone (PCL) and lactic acid and other aliphatic hydroxyl carboxylic acids
Copolymer (poly (glycolide-lactide) (PGLA) etc.), be derived by aliphatic dihydroxy alcohol and aliphatic/aromatic dicarboxylic acids
Aliphatic/aromatic polyester (poly butylene succinate (PBS), polyadipate/terephthalic acid (TPA)-fourth diester (PBAT) etc.)
Deng polyester.
These biodegradable polymers are under compost, seawater moderate condition, by the effect of microorganism in nature,
Obvious degradation can be occurred as soon as in several weeks, achieves that within 6-12 months that basic degraded is complete.Meanwhile, catabolite turn into human body without
The small molecules such as harmful lactic acid, carbon dioxide, water.
Particularly, the raw material of polylactic acid base polymer is from the lactic acid obtained by the amylofermentations such as corn, cassava, total carbon emissions
It is few, and raw material is renewable, and particularly attract attention.
But all there are its advantage and disadvantage in the biodegradable polyesters of these large-scale productions.For example, PLA (PLA)
Because its is crisp, hard, lack the characteristic of pliability, therefore it utilizes and is only limitted to hard formed products；And poly butylene succinate
(PBS), polyadipate/terephthalic acid (TPA)-fourth diester (PBAT) then mainly shows preferable toughness, but in hardness and rigidity
There is larger defect in aspect, be suitable only for doing thin-film material.Therefore in order to realize the combination property of biodegradable polymer material
Improve, often by the way of two or more biodegradable polymer is compound, obtain degradable polyester alloy.
However, various biodegradable polyesters but present obvious thermodynamics incompatible appearance.Simultaneously as degradable
The thermal instability of polyester, is influenceed by high shear when screw rod is processed, is extremely easy in decomposition.Therefore, to realize that thermodynamics is incompatible
Different high polymer materials each superior performance is overlapped, compatilizer and compatible technique become high polymer alloy technology
It is crucial.
In recent years, all have both at home and abroad in terms of biodegradable polyesters are modified compatilizer and compatible technique new trial with into
Really.Beautiful et al. bulking agent (the Chinese patent CN reported with hyperbranched triazine as PLA/PBAT co-mixing systems of Jin Yu
104194294A)；Shanghai Genius New Material (Group) Co., Ltd. is then reported using bisoxazoline class chain extender or official
The isocyanates chain extender of energy degree >=2 realizes compatible (the Chinese patent CN 103589124A) to PLA/PBAT.In document also
Once report used macromolecular epoxies chain extender, trade name Lotader AX8900, Joncryl ADR-4368, ADR-4370
Deng raising PLA and PBAT compatibility, and it is extended to the compatibility for improving other biological degradable polyester.But, bisoxazoline
Class chain extender mainly has higher reactivity, hyperbranched triazine chain extender more difficult synthesis in itself, while dioxazole to carboxyl
Quinoline class, hyperbranched triazine and isocyanates these small molecule chain extenders then have certain toxicity, if reaction not exclusively then can
Lead to grave consequences.Although epoxies macromolecular chain extender avoids the defects such as small molecule chain extender is poisonous, but because epoxy radicals
Group needs can just have preferable activity at relatively high temperatures, and temperature is too high polyester is degraded；Macromolecular chain extender makes simultaneously
During, the thermodynamically incompatible problem with polyester base material is equally existed, and then influence alloy property.
The content of the invention
Present invention aims to overcome that prior art defect realizes two kinds and above biodegradable polyesters there is provided a kind of
Alloy and preparation method thereof.
Technical solution of the present invention is based on reactive extrusion technology, and difunctional small molecule and initiator directly are mixed into biology can
In polyester components of degrading, one-step method realizes the polymerization and the reaction of epoxide group and polyester molecule of vinyl.
A kind of biodegradable polyesters alloy, including following components are constituted by weight：
The biodegradable polyesters are by PLA (PLA), polycaprolactone (PCL), Biopol GO 4 (PHB), poly-succinic
In butanediol ester (PBS) or polyadipate/terephthalic acid (TPA)-fourth diester (PBAT) two or more in any proportion
Mixing；
The bulking agent component A is selected from the styrene base class to biodegradable polyesters with certain compatibilization, is free of
The esters of acrylic acid or methyl acrylic ester simple function group small molecule of epoxide group；
The bulking agent component B is selected from the esters of acrylic acid or methyl acrylic ester difunctional for including epoxide group
One or more in micromolecular compound；
The initiator is the one or more in organic peroxide or azo-initiator；
The lubricant is zinc stearate, calcium stearate, odium stearate, magnesium stearate, barium stearate, oleamide, mustard
One or more in sour acid amides, paraffin or Tissuemat E；
The filler is calcium carbonate, kaolin, silica, carbon fiber, mica, montmorillonite, clay, barium carbonate, talcum
One or more in powder, aluminum oxide, barium sulfate or magnesium sulfate.
Further, the mixed proportion of each component can arbitrarily arrange in pairs or groups in biodegradable polyesters of the present invention, it is only necessary to two
Plant and the mixing of two or more biodegradable polyesters.
Further, bulking agent component A of the present invention is specially styrene, EMA, methacrylic acid fourth
One kind in ester, lauryl methacrylate, octadecyl methacrylate, butyl acrylate or lauryl acrylate or one
More than kind.
Further, bulking agent component A of the present invention is preferably styrene, EMA or methacrylic acid
Butyl ester.
Further, bulking agent component B of the present invention is recommended as GMA, glycidyl
One or more in propyl ester or Glycidyl Acrylate.
Further, initiator of the present invention be cyclohexanone peroxide, cumyl peroxide, di-t-butyl peroxide,
One or more in ABVN.
Further, described lubricant is preferably calcium stearate, barium stearate or oleamide.
Further, described filler is preferably calcium carbonate, talcum powder or silica.
Further, biodegradable polyesters alloy of the present invention, recommendation is made up of by weight following components：
The biodegradable polyesters are by PLA (PLA), polycaprolactone (PCL), Biopol GO 4 (PHB), poly-succinic
In butanediol ester (PBS) or polyadipate/terephthalic acid (TPA)-fourth diester (PBAT) two or more in any proportion
Mixing；Described bulking agent component A is styrene, EMA or butyl methacrylate；Described bulking agent group
Point B be one kind in GMA, GMA or Glycidyl Acrylate or it is a kind of with
On；Described initiator is one or both of cyclohexanone peroxide, cumyl peroxide or di-t-butyl peroxide；Institute
Lubricant is stated for calcium stearate, barium stearate or oleamide；Described filler is calcium carbonate, talcum powder or silica.
Further, biodegradable polyesters alloy of the present invention, is most preferably made up of by weight following components：
The biodegradable polyesters be PLA, polycaprolactone, Biopol GO 4, poly butylene succinate or gather oneself two
Acid/terephthalic acid (TPA)-fourth diester；Described bulking agent component A is styrene；Described bulking agent component B is methacrylic acid
Ethylene oxidic ester；Described initiator is di-t-butyl peroxide；The lubricant is calcium stearate or barium stearate；Described
Filler is calcium carbonate or talcum powder.
In addition, the present invention also provides a kind of preparation method of described biodegradable polyesters alloy, comprise the following steps：
(1) biodegradable polyesters and filler are separately dried processing；
(2) bulking agent component A and component B are washed with dilute solution of sodium hydroxide respectively, drying process；
(3) each component is weighed according to proportioning, after the biodegradable polyesters after step (1) processing and step (2) processing
Bulking agent component A, bulking agent component B be well mixed with initiator, lubricant, filler；
(4) material mixed is added to melting mixing in double screw extruder, extruding pelletization；
(5) step (4) is extruded to obtained pellet drying process, and encapsulated.
Usually, biodegradable polyesters drying process described in step (1) is is dried in vacuo, 60-80 DEG C of drying temperature,
Drying time is 6-24h；Described paddle dryer is processed as conventional air blast drying, 100-120 DEG C of drying temperature, and drying time is
10-24h。
Further, in step (2) bulking agent component A and component B washings dilute solution of sodium hydroxide concentration used is 1-
10%, wash temperature is room temperature；Dry and dried for room temperature two-stage, be calcium chloride, second level drier from first order drier
For molecular sieve.
Generally, the extrusion temperature of double screw extruder is recommended as 120-200 DEG C, screw speed 60- described in step (4)
600rpm, screw slenderness ratio L/D are 36-54:1.
The drying process of pellet described in step (5) is recommended as vacuum drying, 60-80 DEG C of drying temperature, and drying time is
1-4h。
It not only can be very good to improve the component of biodegradable polyester blend two or even many using technical solution of the present invention
Compatibility between component, the thermodynamics overcome between macromolecular epoxies chain extender and degradable polyester is incompatible, Er Qiesuo
Obtained biodegradable polyesters alloy integrates each component performance, small molecule noresidue.This kind of alloy property can be under
The performance indications requirement of trip product is adjusted, and can be applied to the multiple fields such as polybag, wire rod, sheet material.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Experimental raw used in embodiment：
PLA：PLA, Natureworks companies provide, and the trade mark is respectively 4032D, 2003D；The PLA of this two trades mark
Raw material be lactic acid, wherein D-ALPHA-Hydroxypropionic acid content<5%, weight average molecular weight MwScope is 5-20 ten thousand.
PBAT：It is used in poly- (terephthalic acid (TPA)/adipic acid butanediol) ester, embodiment to be produced for BASF Aktiengesellschaft,
Trade mark Ecoflex-F-Blend-C1200, weight average molecular weight MwFor 100,000.
PBS：It is used for BASF Aktiengesellschaft's production, trade mark HF1400 in the fat of poly-succinic fourth two, embodiment.
PCL：It is used for the production of Bo Situo companies of Sweden, trade mark Capa6800, weight average molecular weight in polycaprolactone, embodiment
MwFor 80,000.
PHB：It is used for BASF Aktiengesellschaft's production, trade mark MD1001 in poly(hydrobutyl ester), embodiment.
Mechanics Performance Testing：Tensile property testing standard is national standard GBT1040.2-2006, and impact property testing standard is
National standard GB1043.1-2008.
Embodiment 1
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of calcium stearate, 10 parts of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 2
(1) PLA (4032D) and PBS is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Aerosil
The drying process 12h in 120 DEG C of convection ovens；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 88 parts of PLA, 12 parts of PBS, 0.4 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of calcium stearate, 5 parts of aerosils, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 170 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=40/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 3
(1) by PLA (4032D), PBAT and PBS vacuum drying, 60 DEG C of drying temperature, drying time is 12h；Carbon fiber
T500 drying process 6h in 120 DEG C of convection ovens；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 85 parts of PLA, 10 parts of PBAT, 5 parts of PBS are taken, 0.5 part of styrene, 0.5 part of GMA,
0.02 part of cumyl peroxide, 0.1 part of calcium stearate, 5 parts of carbon fiber T500, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 175 DEG C of areas, three 190 DEG C of areas, four 200 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 4
(1) by PLA (4032D), PBAT and PCL vacuum drying, 60 DEG C of drying temperature, drying time is 12h；Carbon fiber
T500 drying process 6h in 120 DEG C of convection ovens；
(2) lauryl methacrylate and GMA are washed with dilute solution of sodium hydroxide respectively,
Then drying process；
(3) 80 parts of PLA, 15 parts of PBAT, 5 parts of PCL, 0.5 part of lauryl methacrylate, 0.5 part of methacrylic acid contracting are taken
Water glyceride, 0.02 part of cumyl peroxide, 0.1 part of calcium stearate, 5 parts of carbon fiber T500, normal temperature is mixed in high mixer
5min；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 190 DEG C of areas, four 200 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 1-4 pellet enters after injection molding, the performance test such as table 1 below of standard batten.
The embodiment 1-4 the performance test results of table 1.
From table 1 it can be found that not only have by modified biodegradable polyesters alloy higher tensile strength and
Impact strength, while elongation at break also increases, such material can be used for preparing 3D printing wire rod, the product such as sheet material.
Embodiment 5
(1) by PLA (4032D), PLA (2003D) and PBAT vacuum drying, 60 DEG C of drying temperature, drying time is 12h；
Talcum powder drying process 6h in 120 DEG C of convection ovens；
(2) lauryl acrylate and methylpropenoic acid epoxypropane ester are washed with dilute solution of sodium hydroxide respectively, then
Drying process；
(3) 50 parts of PLA (4032D), 40 parts (2003D), 10 parts of PBAT, 0.5 part of lauryl methacrylate, 0.25 part are taken
Methylpropenoic acid epoxypropane ester, 0.01 part of cyclohexanone peroxide, 0.1 part of calcium stearate, 10 parts of talcum powder, in high mixer often
Temperature mixing 5min；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 170 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 6
(1) PLA (4032D) and PHB is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is at 120 DEG C
Drying process 6h in convection oven；
(2) butyl methacrylate and Glycidyl Acrylate are washed with dilute solution of sodium hydroxide respectively, then dried
Processing；
(3) 90 parts of PLA, 10 parts of PHB, 0.5 part of butyl methacrylate, 0.25 part of Glycidyl Acrylate, 0.02 part are taken
ABVN, 0.1 part of zinc stearate, 10 parts of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 190 DEG C of areas, four 200 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=40/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 7
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Aluminum oxide is 120
Drying process 6h in DEG C convection oven；
(2) octadecyl methacrylate and GMA are washed with dilute solution of sodium hydroxide respectively
Wash, then drying process；
(3) 60 parts of PLA, 40 parts of PBAT, 1 part of octadecyl methacrylate, 0.5 part of methyl propenoic acid glycidyl are taken
Ester, 0.04 part of di-t-butyl peroxide, 0.1 part of ethylene waxes, 8 parts of aluminum oxide, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 170 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=40/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 8
(1) PLA (2003D) and PBS is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Kaolin is at 120 DEG C
Drying process 6h in convection oven；
(2) EMA and GMA are washed with dilute solution of sodium hydroxide respectively, so
Drying process afterwards；
(3) 80 parts of PLA are taken, 20 parts of PBS, 1.5 parts of EMAs, 0.5 part of GMA,
0.02 part of cumyl peroxide, 0.1 part of erucyl amide, 10 parts of kaolin, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=38/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 9
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Mica is at 120 DEG C
Drying process 6h in convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.05 part of styrene, 0.05 part of GMA, 0.02 part are taken
Cumyl peroxide, 0.1 part of calcium stearate, 10 parts of micas, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 10
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Barium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) butyl acrylate and GMA are washed with dilute solution of sodium hydroxide respectively, Ran Hougan
Dry processing；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.03 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of sodium stearate, 10 parts of barium carbonates, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 11
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Barium sulfate is 120
Drying process 6h in DEG C convection oven；
(2) lauryl acrylate and GMA are washed with dilute solution of sodium hydroxide respectively, then
Drying process；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.03 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of magnesium stearate, 10 parts of barium sulfate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 12
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Magnesium sulfate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.3 part of styrene, 0.1 part of GMA, 0.05 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of barium stearate, 10 parts of magnesium sulfate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 13
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Montmorillonite is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 2.5 parts of GMAs, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of oleamide, 10 parts of montmorillonites, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 14
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 10 parts of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 15
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Clay is at 120 DEG C
Drying process 6h in convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 3 parts of paraffin, 1 part of clay, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 16
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.05 part of calcium stearate, 20 parts of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 17
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.5 part of calcium stearate, 40 parts of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 18
(1) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(2) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(3) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 3 parts of calcium stearates, 1 part of calcium carbonate, the normal temperature mixing 5min in high mixer；
(4) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(5) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Embodiment 19
(6) PLA (4032D) and PBAT is dried in vacuo, 60 DEG C of drying temperature, drying time is 12h；Calcium carbonate is 120
Drying process 6h in DEG C convection oven；
(7) styrene and GMA are washed with dilute solution of sodium hydroxide respectively, then at drying
Reason；
(8) 90 parts of PLA, 10 parts of PBAT, 0.5 part of styrene, 0.25 part of GMA, 0.02 part of mistake are taken
Aoxidize diisopropylbenzene (DIPB), 0.1 part of calcium stearate, 0 part of calcium carbonate, the normal temperature mixing 5min in high mixer；
(9) obtained mixture is added to melting mixing in double screw extruder, reactive extrursion granulation, dual-screw-stem machine is each
Area's temperature is：One 160 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, 180 DEG C of head；Screw speed
For 200rpm, draw ratio L/D=44/1, the tie rod type of cooling：20 meters air-cooled；
(10) 2h will be dried in vacuo at 60 DEG C of pellet obtained by step (4), encapsulated.
Claims (10)
1. a kind of biodegradable polyesters alloy, the biodegradable polyesters alloy includes following components group by weight
Into：
The biodegradable polyesters by PLA, polycaprolactone, Biopol GO 4, poly butylene succinate or polyadipate/
Two or more in terephthalic acid (TPA)-fourth diester is mixed in any proportion；
The bulking agent component A, which is selected from, has the styrene base class of certain compatibilization to biodegradable polyesters, without epoxy
The esters of acrylic acid or methyl acrylic ester simple function group small molecule of group；
The bulking agent component B is selected from the esters of acrylic acid or small point of methyl acrylic ester difunctional for including epoxide group
One or more in sub- compound；
The initiator is the one or more in organic peroxide or azo-initiator；
The lubricant is zinc stearate, calcium stearate, odium stearate, magnesium stearate, barium stearate, oleamide, erucic acid acyl
One or more in amine, paraffin or Tissuemat E；
The filler is calcium carbonate, kaolin, silica, carbon fiber, mica, montmorillonite, clay, barium carbonate, talcum powder, oxygen
Change the one or more in aluminium, barium sulfate or magnesium sulfate.
2. biodegradable polyesters alloy as claimed in claim 1, it is characterised in that：The bulking agent component A be styrene,
EMA, butyl methacrylate, lauryl methacrylate, octadecyl methacrylate, acrylic acid fourth
One or more in ester or lauryl acrylate.
3. biodegradable polyesters alloy as claimed in claim 2, it is characterised in that：The bulking agent component A lubricants are
Calcium stearate, barium stearate or oleamide.
4. biodegradable polyesters alloy as claimed in claim 1, it is characterised in that：The bulking agent component B is methyl-prop
One or more in olefin(e) acid ethylene oxidic ester, GMA or Glycidyl Acrylate.
5. biodegradable polyesters alloy as claimed in claim 1, it is characterised in that：The initiator is peroxidating hexamethylene
One or more in ketone, cumyl peroxide, di-t-butyl peroxide, ABVN.
6. biodegradable polyesters alloy as claimed in claim 1, it is characterised in that the biodegradable polyesters alloy by
Following components is constituted by weight：
The biodegradable polyesters by PLA, polycaprolactone, Biopol GO 4, poly butylene succinate or polyadipate/
Two or more in terephthalic acid (TPA)-fourth diester is mixed in any proportion；Described bulking agent component A be styrene,
EMA or butyl methacrylate；Described bulking agent component B is GMA, methyl-prop
One or more in olefin(e) acid polyglycidyl or Glycidyl Acrylate；Described initiator is cyclohexanone peroxide, mistake
Aoxidize one or both of diisopropylbenzene (DIPB) or di-t-butyl peroxide；The lubricant is calcium stearate, barium stearate or oil
Sour acid amides；Described filler is calcium carbonate, talcum powder or silica.
7. a kind of preparation method of biodegradable polyesters alloy as claimed in claim 1, it is characterised in that methods described bag
Include following steps：
(1) biodegradable polyesters and filler are separately dried processing；
(2) bulking agent component A and component B are washed with dilute solution of sodium hydroxide respectively, drying process；
(3) each component is weighed according to proportioning, by the increasing after the biodegradable polyesters after step (1) processing and step (2) processing
Hold agent component A, bulking agent component B to be well mixed with initiator, lubricant, filler；
(4) material mixed is added to melting mixing in double screw extruder, extruding pelletization；
(5) step (4) is extruded to obtained pellet drying process, and encapsulated.
8. the preparation method of biodegradable polyesters alloy as claimed in claim 7, it is characterised in that：Institute in step (4)
The extrusion temperature for stating double screw extruder is 120-200 DEG C, screw speed 60-600rpm, and screw slenderness ratio L/D is 36-54:1.
9. the preparation method of biodegradable polyesters alloy as claimed in claim 7, it is characterised in that：Institute in step (1)
It is vacuum drying to state the drying process of biodegradable polyesters, and 60-80 DEG C of drying temperature, drying time is 6-24h；Described fills out
Expect that drying process is dried for conventional air blast, 100-120 DEG C of drying temperature, drying time is 10-24h.
10. the preparation method of biodegradable polyesters alloy as claimed in claim 7, it is characterised in that：Institute in step (5)
It is vacuum drying to state the drying process of pellet, and 60-80 DEG C of drying temperature, drying time is 1-4h.
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| CN201710491615.2A CN107118309A (en) | 2017-06-26 | 2017-06-26 | A kind of biodegradable polyesters alloy and preparation method thereof |
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| CN201710491615.2A CN107118309A (en) | 2017-06-26 | 2017-06-26 | A kind of biodegradable polyesters alloy and preparation method thereof |
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| CN109553934A (en) * | 2018-10-25 | 2019-04-02 | 南京五瑞生物降解新材料研究院有限公司 | Using the PBS/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation |
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| CN114479388A (en) * | 2022-03-23 | 2022-05-13 | 苏州浩钶环保新材料有限公司 | Biodegradable film blowing material capable of recycling reclaimed materials and preparation method thereof |
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