CN115785632B - High-fluidity high-toughness PLA/PBS (polylactic acid/Poly Butylene succinate) blending alloy material and preparation method thereof - Google Patents
High-fluidity high-toughness PLA/PBS (polylactic acid/Poly Butylene succinate) blending alloy material and preparation method thereof Download PDFInfo
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 84
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 55
- 238000002156 mixing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 16
- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 27
- -1 polybutylene succinate Polymers 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229960004109 potassium acetate Drugs 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims 1
- 235000013904 zinc acetate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses a high-fluidity high-toughness PLA/PBS blend alloy material and a preparation method thereof. The high-fluidity high-toughness PLA/PBS blend alloy material comprises the following raw materials in parts by mass: 30-80 parts of polylactic acid, 20-70 parts of polybutylene succinate and 5-20 parts of compatilizer; the preparation method of the compatilizer comprises the following steps: mixing 30-80 parts by mass of PLA, 20-70 parts by mass of PBS and 0.3-0.7 part by mass of acetate uniformly, and then carrying out melt extrusion granulation by a double screw extruder to obtain the compatilizer. The preparation method of the high-fluidity high-toughness PLA/PBS blend alloy material comprises the following steps: and uniformly mixing polylactic acid, polybutylene succinate and a compatilizer, and then carrying out melt extrusion by a double-screw extruder to obtain the high-fluidity high-toughness PLA/PBS blend alloy material.
Description
Technical Field
The invention relates to the technical field of PLA/PBS (polylactic acid/Poly Bus) blending alloy materials, in particular to a high-fluidity high-toughness PLA/PBS blending alloy material and a preparation method thereof.
Background
With the continuous development and progress of human society, the demands and the use of plastic products are greatly improved, a large amount of waste plastic is introduced into the life of people, the pollution to the ground, air and sea is increasingly serious, and the great development and popularization of biodegradable materials become a great trend for solving the plastic pollution problem at present.
Polylactic acid (PLA) is a plastic which can be plasticized by heating, has high strength and can be completely biodegraded, is widely applied to the fields of injection molding and extrusion, has good biocompatibility and degradability, but has high brittleness and low impact strength, and greatly limits the application of the polylactic acid.
Polybutylene succinate (PBS) has good crystallinity, toughness and biodegradability and is widely applied to the fields of food packaging and the like.
Polybutylene succinate (PBS) can be added into polylactic acid (PLA) to improve the toughness of the PLA and prepare 100 percent biodegradable high-toughness PLA/PBS alloy, but PLA and PBS have extremely poor compatibility, and serious extrusion expansion phenomenon can occur in processing to influence the processability of the material, so that the compatibility of the PLA and the PBS needs to be improved to prepare the high-fluidity high-toughness PLA/PBS alloy.
The patent specification with publication number CN 104292785A discloses a recycled paper fiber polylactic acid composite material, which comprises the following components in percentage by mass: 20-40wt% of polylactic acid, 15-30wt% of recycled paper fiber, 25-35wt% of aliphatic polyester and 10-25wt% of polyurethane thermoplastic elastomer. The material also comprises 1.5-2.5wt% of polylactic acid-cellulose grafting compatilizer and 1.2-2.0wt% of transesterification catalyst, wherein the mass of the transesterification catalyst is the sum of polylactic acid, aliphatic polyester and polyurethane thermoplastic elastomer. Wherein the aliphatic polyester is one or more of polycaprolactone, polybutylene succinate and polybutylene adipate, and the transesterification catalyst is dibutyl tin oxide, dioctyl tin oxide or the combination of dibutyl tin oxide and dioctyl tin oxide.
The patent specification with publication number CN 112778721A discloses a high-toughness hydrolysis-resistant PLA material which comprises the following raw materials in parts by weight: 60-65 parts of polylactic acid PLA, 20-25 parts of at least one of flexible degradable plastic PBAT, PBS or PES and 8-10 parts of inorganic compatilizer. Wherein the inorganic compatilizer is nano-CaCO 3 Or silicon carbide SiC.
Disclosure of Invention
The invention provides a high-fluidity high-toughness PLA/PBS blending alloy material, firstly, a PLA/PBS compatilizer is prepared, and an ester exchange reaction of PLA and PBS in a melt extrusion process of the compatilizer is promoted by acetate to obtain an alloy compatilizer containing a large amount of lactic acid-succinic acid-butanediol chain segments, and the acetate in the compatilizer is excessive, so that on one hand, the molecular weight of the compatilizer is lower, the fluidity of the compatilizer is improved, and further, the fluidity of a final alloy product is improved, and on the other hand, the compatilizer still has a partial ester exchange catalysis effect, the ester exchange reaction of polylactic acid, polybutylene succinate and the compatilizer is promoted, and the compatibility is further improved.
The specific technical scheme is as follows:
the high-fluidity high-toughness PLA/PBS blending alloy material comprises the following raw materials in parts by mass:
30-80 parts of polylactic acid,
20-70 parts of poly (butylene succinate),
5-20 parts of compatilizer;
the preparation method of the compatilizer comprises the following steps: mixing 30-80 parts by mass of PLA, 20-70 parts by mass of PBS and 0.3-0.7 part by mass of acetate uniformly, and then carrying out melt extrusion granulation by a double screw extruder to obtain the compatilizer.
The invention adopts acetate as the transesterification catalyst, and can still show high catalytic efficiency under low addition. The inventor tries catalysts such as tetrabutyl titanate, dibutyl tin oxide, dioctyl tin oxide, bismuth titanate and the like, and as a result, the inventor finds that the catalyst has no catalytic effect under the condition of low addition amount, and secondly, the degradable plastics such as PLA/PBS and the like can be widely applied to the catering field, and certain food-grade requirements are strict on heavy metals such as tin/bismuth and the like, and the tin/bismuth catalyst is easy to carry out complexation reaction with certain auxiliary agents such as certain UV-resistant auxiliary agents, certain antioxidants and the like, so that the effect of the auxiliary agents is reduced, obvious color reaction can occur, and the performance and the appearance of the material are influenced.
In the technical scheme of the invention, the acetate is very small in dosage proportion relative to the polylactic acid and the polybutylene succinate, if the acetate is directly added into the polylactic acid and the polybutylene succinate for blending and melt extrusion in one step, the dispersibility of the acetate is poor, so that the compatilizer generated by transesterification in a final alloy product is unevenly dispersed, the batch stability is poor, and the product production and the client processing are difficult. The invention adopts a mode of preparing the compatilizer containing excessive acetate, so that the acetate has a slightly excessive proportion in the compatilizer, which is similar to the preparation of acetate master batch and then the preparation of blend alloy, improves the dispersibility of the acetate and solves the technical problems.
It should be noted that if acetate is added in the respective production process of the two raw materials, namely polylactic acid and poly butylene succinate, the reaction process is seriously affected, so that the molecular weight of the polylactic acid and poly butylene succinate is reduced, and the performance of the final alloy product is reduced.
The number average molecular weight of the compatilizer is 30000-80000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 500-1500g/10min. The PLA/PBS compatilizer prepared by acetate with higher proportion is a high-fluidity plastic alloy, is similar to a high-fluidity melt-blown material, has no precipitation problem, has extremely close processing temperature and lower melting point of PLA and PBS, can be well plasticized, contains a certain amount of acetate, can continuously carry out a part of transesterification reaction, and further improves the compatibility and fluidity of the final alloy, so that the introduction of the high-fluidity alloy compatilizer can not cause uneven dispersion of materials.
In a preferred embodiment, the compatibilizing agent is prepared by a process wherein the twin-screw extruder has a screw aspect ratio of 44-56:1.
In a preferred embodiment, the compatibilizing agent is prepared by a method wherein the twin-screw extruder has a screw speed of 200 to 300rpm.
In a preferred embodiment, in the preparation method of the compatilizer, the twin-screw extruder is provided with 13 heating zones, and the temperature of each zone from the feeding port to the machine head is as follows: the first area temperature is 160-190 ℃, the second area temperature is 190-220 ℃, the third area temperature is 190-220 ℃, the fourth area temperature is 190-220 ℃, the fifth area temperature is 180-210 ℃, the sixth area temperature is 170-200 ℃, the seventh area temperature is 170-200 ℃, the eighth area temperature is 170-200 ℃, the ninth area temperature is 160-190 ℃, the tenth area temperature is 160-190 ℃, the eleventh area temperature is 160-190 ℃, the twelve area temperature is 160-190 ℃ and the thirteenth area temperature is 200-220 ℃.
In a preferred embodiment, the compatibilizing agent is prepared by a method wherein the sum of the parts by mass of PLA and PBS is 100 parts.
In a preferred embodiment, the sum of the mass parts of the polylactic acid and the polybutylene succinate in the raw material composition of the high-fluidity high-toughness PLA/PBS blend alloy material is 100 parts.
The invention also provides a preparation method of the high-fluidity high-toughness PLA/PBS blend alloy material, which comprises the following steps: and uniformly mixing polylactic acid, polybutylene succinate and a compatilizer, and then carrying out melt extrusion by a double-screw extruder to obtain the high-fluidity high-toughness PLA/PBS blend alloy material.
In a preferred embodiment, in the method for preparing the high-fluidity high-toughness PLA/PBS blend alloy material, the length-diameter ratio of the screws of the double-screw extruder is 44-56:1.
In a preferred embodiment, in the method for preparing the high-fluidity high-toughness PLA/PBS blend alloy material, the screw speed of the twin-screw extruder is 200-300rpm.
In a preferred embodiment, in the method for preparing the high-fluidity high-toughness PLA/PBS blend alloy material, the twin-screw extruder is provided with 13 heating zones, and the temperature of each zone from the feeding port to the machine head is as follows: the first area temperature is 160-190 ℃, the second area temperature is 190-220 ℃, the third area temperature is 190-220 ℃, the fourth area temperature is 190-220 ℃, the fifth area temperature is 180-210 ℃, the sixth area temperature is 170-200 ℃, the seventh area temperature is 170-200 ℃, the eighth area temperature is 170-200 ℃, the ninth area temperature is 160-190 ℃, the tenth area temperature is 160-190 ℃, the eleventh area temperature is 160-190 ℃, the twelve area temperature is 160-190 ℃ and the thirteenth area temperature is 200-220 ℃.
In a preferred embodiment, in the preparation method of the high-fluidity high-toughness PLA/PBS blend alloy material, the feeding port and the exhaust port of the twin-screw extruder are protected by dry nitrogen.
Compared with the prior art, the invention has the beneficial effects that:
1) The PLA and the PBS both contain a large amount of ester bonds, and the ester exchange activity of the PLA and the PBS is greatly catalyzed by the introduction of acetate in the melt blending process, so that the excessive acetate fully performs the ester exchange reaction to obtain the alloy compatilizer containing a large amount of lactic acid-succinic acid-butanediol chain segments.
2) The compatilizer, PLA and PBS are simultaneously melt-blended and processed, the compatilizer has good compatibility with the PLA and the PBS, and a small amount of acetate contained in the compatilizer can generate new catalysis in the melt-blending process of the PLA and the PBS, so that the compatibility of the PLA and the PBS is further improved.
3) The compatilizer prepared by the method of the invention is applicable to PLA/PBS blending processing with any proportion because of the raw materials thereof, and can be used as acetate master batch because of the excessive acetate used in the compatilizer, and can be dispersed more uniformly when the adding amount of the acetate is extremely small, so that the overall stability of the alloy is greatly improved.
4) When the raw materials of PLA and PBS are produced, acetate is added to seriously influence the reaction process, so that the molecular weight is reduced, the performance is reduced, the problems can be avoided by adding acetate by the method, and whether the transesterification reaction is excessive or not can be controlled by adjusting the using amount of acetate.
5) The compatilizer prepared by the method of the invention has the advantages that the molecular weight of the compatilizer is reduced to a certain extent by introducing excessive acetate, the fluidity is extremely high, and the compatilizer has excellent compatibility with PLA/PBS, so that the compatilizer can play a good plasticizing role by introducing the compatilizer into the PLA/PBS, and the fluidity of the material is improved.
6) The PLA/PBS alloy material prepared by the method is 100% biodegradable because the compatilizer is also the degradable material.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
The amounts "parts" of the components in the following examples and comparative examples refer to parts by mass unless otherwise specified. The preparation method of the compatilizer comprises the following steps: uniformly mixing 70 parts by mass of PLA, 30 parts by mass of PBS and 0.6 part by mass of zinc acetate, and performing melt extrusion granulation by a double screw extruder to obtain a compatilizer Zn; wherein: the length-diameter ratio of the screw of the double-screw extruder is 50:1, the screw rotating speed of the double-screw extruder is 210rpm, the double-screw extruder is provided with 13 heating areas, and the temperatures of the areas from a feeding port to a machine head are as follows: the first area temperature is 160-190 ℃, the second area temperature is 190-220 ℃, the third area temperature is 190-220 ℃, the fourth area temperature is 190-220 ℃, the fifth area temperature is 180-210 ℃, the sixth area temperature is 170-200 ℃, the seventh area temperature is 170-200 ℃, the eighth area temperature is 170-200 ℃, the ninth area temperature is 160-190 ℃, the tenth area temperature is 160-190 ℃, the eleventh area temperature is 160-190 ℃, the twelve area temperature is 160-190 ℃ and the thirteenth area temperature is 200-220 ℃. The number average molecular weight of the compatilizer-Zn is 56000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 857g/10min.
In the preparation method of the compatilizer, under the condition that other conditions are not changed, zinc acetate is replaced by sodium acetate, potassium acetate, calcium acetate and magnesium acetate with equal parts by weight respectively to obtain the compatilizer-Na, the compatilizer-K, the compatilizer-Ca and the compatilizer-Mg, wherein: the number average molecular weight of the compatilizer Na is 60000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 729g/10min; the number average molecular weight of the compatilizer-K is 58000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 775g/10min; the number average molecular weight of the compatilizer Ca is 68000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 683g/10min; the number average molecular weight of the compatilizer Mg is 55000g/mol, and the melt index under the conditions of 190 ℃ and 5kg pressure is 892g/10min.
In the following examples and comparative examples, the length-diameter ratio of the screw of the twin-screw extruder used was 50:1, the screw rotation speed of the twin-screw extruder was 210rpm, the twin-screw extruder was provided with 13 heating zones, and the temperatures of the zones from the feeding port to the head were: the temperature of the first area is 160-190 ℃, the temperature of the second area is 190-220 ℃, the temperature of the third area is 190-220 ℃, the temperature of the fourth area is 190-220 ℃, the temperature of the fifth area is 180-210 ℃, the temperature of the sixth area is 170-200 ℃, the temperature of the seventh area is 170-200 ℃, the temperature of the eighth area is 170-200 ℃, the temperature of the ninth area is 160-190 ℃, the temperature of the tenth area is 160-190 ℃, the temperature of the eleventh area is 160-190 ℃, the temperature of the twelve area is 160-190 ℃, the temperature of the thirteenth area is 200-220 ℃, and the feeding inlet and the exhaust port of the double screw extruder are protected by dry nitrogen.
In the following examples and comparative examples, the impact strength test was carried out using a plastic cantilever impact strength standard ASTM D256-2010, wherein the pendulum energy is 5.5J, the test bars are 5 samples with a thickness of 3.3+ -0.05 mm and a width of 11+ -0.5 mm, and the median value is taken; the tensile strength and elongation at break test adopts a standard experiment method GB-T528-2009 for the tensile properties of vulcanized rubber and thermoplastic elastomer rubber, wherein the gauge length is 25mm, the tensile rate is 500mm/min, the test sample strip is 5 dumbbell-shaped sample strips with the thickness of 2+/-0.1 mm and the width of 6+/-0.1 mm, and the middle value is taken; melt index testing was conducted using the melt flow rate test Standard ASTM D1238-20, at 190 ℃/5kg. The above test environments were all conducted at 23.+ -. 1 ℃ and 50.+ -. 5% RH.
Example 1
Weighing 70 parts of PLA and 30 parts of PBS;
2 parts of compatilizer Zn and the materials are placed in a stirrer to be fully mixed, and fed into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 54.3MPa, an elongation at break of 8%, an impact strength of 28J/M, and a 190 ℃/5kg melt index of 31.4g/10min.
Example 2
Weighing 70 parts of PLA and 30 parts of PBS;
6 parts of compatilizer Zn and the materials are placed in a stirrer to be fully mixed, and fed into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 62.5MPa, an elongation at break of 20%, an impact strength of 53J/M, and a 190 ℃/5kg melt index of 112.5g/10min.
Example 3
Weighing 70 parts of PLA and 30 parts of PBS;
placing 9 parts of compatilizer Zn and the materials in a stirrer for fully mixing, and feeding the materials into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 58.5MPa, an elongation at break of 13%, an impact strength of 39J/M, and a 190 ℃/5kg melt index of 312.2g/10min.
Example 4
Weighing 70 parts of PLA and 30 parts of PBS;
placing 9 parts of compatilizer Na and the materials in a stirrer for fully mixing, and feeding the materials into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 59.7MPa, an elongation at break of 15%, an impact strength of 37J/M, and a 190 ℃/5kg melt index of 288.3g/10min.
Example 5
Weighing 70 parts of PLA and 30 parts of PBS;
placing 9 parts of compatilizer-K and the materials in a stirrer for fully mixing, and feeding the materials into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 55.6MPa, an elongation at break of 13%, an impact strength of 42J/M, and a 190 ℃/5kg melt index of 297.1g/10min.
Example 6
Weighing 70 parts of PLA and 30 parts of PBS;
placing 9 parts of compatilizer-Ca and the materials in a stirrer for fully mixing, and feeding the materials into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 55.6MPa, an elongation at break of 15%, an impact strength of 36J/M, and a 190 ℃/5kg melt index of 265.3g/10min.
Example 7
Weighing 70 parts of PLA and 30 parts of PBS;
9 parts of compatilizer-Mg and the materials are placed in a stirrer to be fully mixed, and fed into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain the high-fluidity high-toughness PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this example had a tensile strength of 55.6MPa, an elongation at break of 13%, an impact strength of 37J/M, and a 190 ℃/5kg melt index of 333.2g/10min.
Comparative example 1
Weighing a certain amount of PLA particles, and drying the PLA particles to obtain moisture;
PLA pellets were injection molded and tested.
PLA pellets obtained in this comparative example had a tensile strength of 64MPa, an elongation at break of 0%, an impact strength of 11J/M, and a 190 ℃/5kg melt index of 9g/10min.
Comparative example 2
Weighing 70 parts of PLA and 30 parts of PBS, putting the PLA and the PBS into a stirrer, fully mixing, and feeding the mixture into a double-screw extruder through a feeding port;
and (3) after exiting the die head, carrying out bracing granulation, and drying at 100 ℃ to obtain PLA/PBS blending alloy material particles.
The PLA/PBS blend alloy material prepared in this comparative example had a tensile strength of 52.7MPa, an elongation at break of 6%, an impact strength of 18J/M, and a 190 ℃/5kg melt index of 15g/10min.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (8)
1. The high-fluidity high-toughness PLA/PBS blending alloy material is characterized by comprising the following raw materials in parts by mass:
30-80 parts of polylactic acid,
20-70 parts of poly (butylene succinate),
5-20 parts of compatilizer;
the sum of the mass parts of polylactic acid and polybutylene succinate in the raw material composition of the high-fluidity high-toughness PLA/PBS blend alloy material is 100 parts;
the preparation method of the compatilizer comprises the following steps: uniformly mixing 30-80 parts by mass of PLA, 20-70 parts by mass of PBS and 0.3-0.7 part by mass of acetate, and performing melt extrusion granulation by a double screw extruder to obtain the compatilizer; in the preparation method of the compatilizer, the sum of the mass parts of PLA and PBS is 100 parts.
2. The high-fluidity high-toughness PLA/PBS blend alloy material according to claim 1, wherein the compatibilizing agent is prepared by the process of:
the length-diameter ratio of the screws of the double-screw extruder is 44-56:1;
the screw rotating speed of the double-screw extruder is 200-300rpm;
the twin-screw extruder is provided with 13 heating zones, and the temperature of each zone from a feeding port to a machine head is as follows: the first area temperature is 160-190 ℃, the second area temperature is 190-220 ℃, the third area temperature is 190-220 ℃, the fourth area temperature is 190-220 ℃, the fifth area temperature is 180-210 ℃, the sixth area temperature is 170-200 ℃, the seventh area temperature is 170-200 ℃, the eighth area temperature is 170-200 ℃, the ninth area temperature is 160-190 ℃, the tenth area temperature is 160-190 ℃, the eleventh area temperature is 160-190 ℃, the twelve area temperature is 160-190 ℃ and the thirteenth area temperature is 200-220 ℃.
3. The high-fluidity high-toughness PLA/PBS blend alloy material according to claim 1, wherein said acetate includes at least one of sodium acetate, potassium acetate, calcium acetate, magnesium acetate, and zinc acetate in the preparation method of said compatibilizer.
4. The high flow high toughness PLA/PBS blend alloy material according to claim 1, wherein the compatibilizing agent has a number average molecular weight of 30000-80000g/mol and a melt index of 500-1500g/10min at 190 ℃ under 5kg pressure.
5. The method for preparing the high-fluidity high-toughness PLA/PBS blend alloy material as claimed in any one of claims 1 to 4, comprising the steps of: and uniformly mixing polylactic acid, polybutylene succinate and a compatilizer, and then carrying out melt extrusion by a double-screw extruder to obtain the high-fluidity high-toughness PLA/PBS blend alloy material.
6. The method according to claim 5, wherein in the method for preparing the high-fluidity high-toughness PLA/PBS blend alloy material, the screw length-diameter ratio of the twin-screw extruder is 44-56:1.
7. The method according to claim 5, wherein the screw speed of the twin-screw extruder is 200-300rpm.
8. The preparation method of the high-fluidity high-toughness PLA/PBS blend alloy material according to claim 5, wherein the preparation method comprises the following steps:
the twin-screw extruder is provided with 13 heating zones, and the temperature of each zone from a feeding port to a machine head is as follows: the first area is 160-190 ℃, the second area is 190-220 ℃, the third area is 190-220 ℃, the fourth area is 190-220 ℃, the fifth area is 180-210 ℃, the sixth area is 170-200 ℃, the seventh area is 170-200 ℃, the eighth area is 170-200 ℃, the ninth area is 160-190 ℃, the tenth area is 160-190 ℃, the eleventh area is 160-190 ℃, the twelve area is 160-190 ℃ and the thirteenth area is 200-220 ℃;
and the feeding port and the exhaust port of the double-screw extruder are protected by dry nitrogen.
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