CN117551340A - PLA composite material with high melt strength and preparation method thereof - Google Patents
PLA composite material with high melt strength and preparation method thereof Download PDFInfo
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- CN117551340A CN117551340A CN202311589634.0A CN202311589634A CN117551340A CN 117551340 A CN117551340 A CN 117551340A CN 202311589634 A CN202311589634 A CN 202311589634A CN 117551340 A CN117551340 A CN 117551340A
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 bis-aminopropyl Chemical group 0.000 claims abstract description 40
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000004626 polylactic acid Substances 0.000 claims description 77
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 76
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- RROBIDXNTUAHFW-UHFFFAOYSA-N benzotriazol-1-yloxy-tris(dimethylamino)phosphanium Chemical compound C1=CC=C2N(O[P+](N(C)C)(N(C)C)N(C)C)N=NC2=C1 RROBIDXNTUAHFW-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 33
- 238000012545 processing Methods 0.000 abstract description 12
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 238000000071 blow moulding Methods 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010096 film blowing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000009471 action Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012824 chemical production Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010102 injection blow moulding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229920006250 telechelic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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
The invention discloses a PLA composite material with high melt strength and a preparation method thereof. The high melt strength PLA composite material comprises the following components: PLA, carboxyl-terminated nitrile rubber, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant and lubricant accelerator. During preparation, the components are put into a double-screw extruder according to the proportion, and extruded and granulated to obtain the PLA composite material particles with high melt strength. The invention can increase the melt strength of the material by chain extension of PLA molecular chains and whisker introduction, and can obtain degradable products with good appearance and physical properties through processing such as blow molding, injection molding, extrusion and the like.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a PLA composite material.
Background
The bio-based degradable polymer material can be derived from animals and plants without depending on increasingly scarce petroleum resources, and can be automatically decomposed under the actions of soil, enzymes and the like to reduce environmental pollution, and the material conforms to the current large trend of global product environmental protection, so that the material is widely focused and studied. Polylactic acid (PLA) is one of the most promising bio-based degradable polymer materials at present, has the advantages of wide sources, good biocompatibility, biodegradability and the like, but has the defects of insufficient mechanical properties, poor thermal stability, low melt strength and the like, so that the application field of the polylactic acid is more limited. Because of few PLA molecular chain branched chains, the melt strength of the material is low, and the strain hardness is insufficient, the processing temperature of polylactic acid is too narrow, and the application in the injection molding and blow molding industries is limited. Therefore, the melt strength of PLA material is improved, the processing stability is improved, the application scene is enlarged, and the added value of the product is increased.
The current methods for improving the melt strength of PLA materials are of the following classes: one is to further polymerize polylactic acid through a plurality of steps in a reaction kettle to improve the molecular weight and further improve the melt strength of the material. Chinese patent CN106633007B discloses a method for preparing a PLA material with high melt strength, in which the PLA material is added into a reaction kettle, and polymerized by a two-step method under the action of a catalyst, the method can effectively improve the melt strength of the PLA material, but the operation is complex, and the processing is difficult; the other is through chain extension crosslinking with substances containing GMA functional groups and acrylate functional groups and polylactic acid molecular chains. For example, chinese patent CN115368717a discloses a preparation method of PLA material with high melt strength, which improves the melt strength of the material by polymerizing with a polyepoxide, but the preparation method is performed in two steps, and a large amount of organic solvent is used in the preparation process, so that the process is complex and has environmental protection problem. Chinese patent CN115926402a discloses a method for preparing injection foamed PLA material, which introduces brominated isobutylene-para-methylstyrene copolymer and carboxyl-terminated polybutadiene polymer into PLA material, and in the extrusion process, hydroxyl on PLA molecular chain and carboxyl at two ends of carboxyl-terminated polybutadiene polymer of telechelic polymer undergo condensation reaction to form micro-crosslinking structure, and simultaneously carboxyl-terminated polybutadiene polymer and brominated isobutylene-para-methylstyrene copolymer undergo copolymerization reaction under the action of vulcanizing agent, so as to further improve melt strength of material, thereby improving foaming effect of material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a PLA composite material with high melt strength and a preparation method thereof. By introducing carboxyl terminated nitrile rubber and double-aminopropyl polydimethylsiloxane into PLA material, carboxyl on PLA molecular chain and carboxyl on carboxyl terminated nitrile rubber molecular chain can react with amine groups at two ends of double-aminopropyl polydimethylsiloxane of remote grasping polymer under the action of high temperature and high shear of a double-screw extruder, chain extension is carried out on PLA molecular chain, and melt strength of the material is greatly improved. In addition, whisker with larger length-diameter ratio is introduced into the system, so that the mechanical property and the melt strength of the PLA material can be further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high melt strength PLA composite material, which comprises the following components: PLA, carboxyl-terminated nitrile rubber, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant, lubricant and accelerator.
The PLA composite material has good processability, can be directly used for injection molding, blow molding and extrusion processing, and has a wider processing interval.
Wherein, in the high melt strength PLA composite material, the PLA content is 60-80 percent, preferably 60-70 percent according to the weight percentage; the content of the carboxyl-terminated nitrile rubber is 5-25%, preferably 5-15%; the content of the bis-aminopropyl polydimethylsiloxane is 3-10%, preferably 5-10%; whisker is 5% -20%, preferably 10% -20%; 0.1% -0.5% of antioxidant, preferably 0.3% -0.5%; 0.3% -3%, preferably 1% -3% of accelerator; the lubricant is 0.2% -0.5%, preferably 0.3% -0.5%.
In a preferred embodiment, the polylactic acid is one or two of L-type polylactic acid and D-type polylactic acid. The melt flow rate of the polylactic acid measured at 190 ℃ and under a load of 2.16kg is 0.2-30g/10min. Preferably, the L-type polylactic acid and the D-type polylactic acid are compounded, wherein the L-type polylactic acid is 90-95%, the D-type polylactic acid is 5-10%, and the melt flow rate of the polylactic acid is 2-20g/10min (190 ℃ C., 2.16 kg).
In a preferred embodiment, the carboxyl terminated nitrile rubber is nitrile rubber powder with carboxyl terminated active functional groups at two ends of a molecular chain, and the Mooney viscosity is 90-140.
The double-aminopropyl polydimethylsiloxane is a macromolecular organosilicon compound, and two ends of a molecular chain contain two-NH 2 A radical having a viscosity of 3000 to 10000, preferably 5000 to 10000, at 25 ℃.
The whisker is inorganic whisker including but not limited to silicon carbide whisker, calcium sulfate whisker, calcium carbonate whisker, basic magnesium sulfate whisker, aluminum oxide whisker and potassium titanate whisker. Preferably, the inorganic whiskers are calcium sulfate whiskers and basic magnesium sulfate whiskers, and the length-diameter ratio of the inorganic whiskers is more than 30.
In a preferred embodiment, the antioxidants include primary antioxidants and secondary antioxidants, the primary antioxidants including, but not limited to, one or more of hindered phenols and hindered amines antioxidants; the secondary antioxidants include, but are not limited to, one or more of thioesters and phosphite antioxidants.
The main antioxidant is preferably pentaerythritol (antioxidant 1010) of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid); the secondary antioxidant of the present invention is preferably tris (2, 4-di-t-butylphenyl) phosphite (antioxidant 168).
The accelerator is one or two of benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate (PyBOP) and benzotriazol-1-yloxy tris (dimethylamino) phosphonium hexafluorophosphate (BOP).
The lubricant is one or more of stearic acid, zinc stearate and magnesium stearate.
The high melt strength PLA composite of the present invention can be processed in equipment known in the art, preferably a twin screw extruder. The method comprises the following steps:
(1) Putting PLA, carboxyl-terminated nitrile rubber powder, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant, accelerator and lubricant raw materials into a high-speed mixer according to the proportion, and mixing for 10-5min to obtain a uniformly mixed premix;
(2) And adding the premix into a single screw extruder bin, and performing extrusion granulation at 170-200 ℃ to obtain PLA composite material particles with high melt strength.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, carboxyl on a PLA molecular chain and carboxyl on the carboxyl-terminated nitrile rubber molecular chain can be subjected to amidation reaction with amino groups at two ends of a remote-grip polymer double-aminopropyl polydimethylsiloxane molecular chain under the action of an accelerator by introducing carboxyl-terminated nitrile rubber and utilizing the high temperature and high shear effects of a double-screw extruder, so that the melt strength of the material is improved, and the processing performance of the material is improved.
(2) According to the invention, carboxyl-terminated nitrile rubber powder is introduced into the PLA material, so that on one hand, the PLA molecular chain can be extended, and in addition, the impact toughness of the material can be obviously improved; meanwhile, by introducing whiskers, the mechanical strength of the material is further improved, and the application range of the material is greatly expanded.
(3) The processing method is simple, PLA composite particles with high melt strength can be prepared through reactive extrusion, and then deep injection foaming processing and film blowing processing can be directly carried out, so that the complex processing process of partial additives in the traditional method is avoided, and the production efficiency is higher.
Drawings
FIGS. 1 and 2 are comparative results of film blowing stability in comparative example 1 and example 1; FIGS. 3 and 4 are comparative results of blown film stability in comparative example 2 and example 2, respectively; fig. 5 and 6 are comparative results of film blowing stability of comparative example 3 and example 3, respectively.
Detailed Description
The invention is further described in connection with the following examples, but the scope of the invention is not limited to the examples only, but also includes any other known modifications within the scope of the claims.
Raw materials:
2003D: PLA, melt index 5g/10min, manufactured by Nature works, U.S.A.;
3001D: PLA, melt index 20g/10min, manufactured by Nature works, U.S.A.;
1072CG: carboxyl terminated nitrile rubber powder produced by Taiwan Nandi.
MQ560: bis-aminopropyl polydimethylsiloxane, viscosity 10000, manufactured by Jiangsu Mu-chi;
CM226: bis-aminopropyl polydimethylsiloxane, viscosity 5000, manufactured by Shanghai;
WS-3D: basic magnesium sulfate whisker with diameter of 1.0um and L/D of >30, and Yingkoukang as produced by science and technology;
RIANOX1010/168: antioxidant, tianjin Li Anlong new material Co.Ltd;
ZnSt: lubricants, hair based chemicals limited;
accelerator PyBOP: purity is more than or equal to 98 percent, and Shanghai terb chemical production is carried out;
accelerator BOP: purity is more than or equal to 98 percent, and Shanghai terb chemical production.
Test method and test equipment
(1) Melt flow rate testing apparatus and method: INSTRON CEAST MF30, tested according to ISO 1133; (2) melt composite viscosity testing equipment and method: GOETTFERT GR20, adding a sample into a charging barrel, and then applying stress to a piston on the charging barrel to enable the piston to pass through a standard die at a certain shear rate so as to measure rheological properties of the material under different conditions;
(3) The film blowing stability evaluation method comprises the following steps: film blowing is carried out by using a film blowing machine, and the film blowing stability is evaluated by measuring the diameter change of film bubbles in the film blowing process;
examples
Modified high melt strength PLA composites of examples 1-5 and comparative examples 1-2 were prepared according to the compounding ratios shown in table 1:
and (3) putting PLA, carboxyl-terminated nitrile rubber, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant, accelerator and lubricant raw materials into a high-speed mixer according to the proportion, mixing for 10-5min, and then extruding and granulating at 190-210 ℃ by adopting a double-screw extruder to obtain PLA composite material particles with high melt strength.
PLA materials of examples 1-5 and comparative examples 1-2 were prepared in the composition ratios shown in Table 1, and then subjected to performance tests, with the specific results shown in tables 2-4.
Table 1 examples 1-5, comparative examples 1-2 proportions and processing conditions
TABLE 2 melt finger and melt viscosity test for each example, comparative example
As can be seen from Table 2, after chain extension of PLA molecular weight, the melt flow rate of the material is reduced, and meanwhile, the compound viscosity of the material is increased, so that the melt strength is obviously improved.
Table 3 shear viscosity test for each example, comparative example
As shown in Table 3, after the PLA molecular chain is extended and the whisker is introduced, the shearing viscosity of the material is obviously improved, which further indicates that the melt strength of the material is improved and the injection foaming performance of the PLA material is greatly improved.
TABLE 4 variation of blown film bubble diameter for examples and comparative examples
From Table 4, it is clear that the stability of the film bubble at the time of film blowing processing is improved after the PLA molecular chain is extended and the whisker is introduced.
As can be seen from the drawing, fig. 1 and fig. 2 show comparison results of film blowing stability of comparative example 1 and example 1, compared with the case that after bis-aminopropyl polydimethylsiloxane is added, in example 1, carboxyl groups on a PLA molecular chain and carboxyl groups on a carboxyl-terminated nitrile rubber molecular chain can be amidated with amino groups at two ends of a remote grasping type polymer bis-aminopropyl polydimethylsiloxane molecular chain under the action of an accelerator, chain extension is performed on the PLA molecular chain, and the film bubble swing amplitude is reduced from 8mm to 1mm during film blowing, so that the film blowing stability is remarkably improved; FIG. 3 and FIG. 4 are comparative results of the blown film stability of comparative example 2 and example 2, respectively, and it can be seen that the stability of the bubble is significantly improved during the blown film after the whisker is introduced by chain extension of PLA molecular chain by bis-aminopropyl polydimethylsiloxane; fig. 5 and fig. 6 are comparative results of the blown film stability of comparative example 3 and example 3, respectively, and it can be seen that the blown film stability cannot be improved due to the lack of the crosslinkable functional group when the carboxyl-terminated nitrile rubber powder (comparative example 3) is not added to the formulation.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (10)
1. A high melt strength PLA composite comprising the following components: PLA, carboxyl-terminated nitrile rubber, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant, lubricant and accelerator.
2. The high melt strength PLA composite material according to claim 1, characterized in that the PLA content is 60% to 80%, preferably 60% to 70% by weight; the content of the carboxyl-terminated nitrile rubber is 5-25%, preferably 5-15%; the content of the bis-aminopropyl polydimethylsiloxane is 3-10%, preferably 5-10%; whisker is 5% -20%, preferably 10% -20%; 0.1% -0.5% of antioxidant, preferably 0.3% -0.5%; 0.3% -3%, preferably 1% -3% of accelerator; the lubricant is 0.2% -0.5%, preferably 0.3% -0.5%.
3. The high melt strength PLA composite of claim 1 or 2, wherein the polylactic acid is one or both of L-type polylactic acid and D-type polylactic acid. The melt flow rate of the polylactic acid measured at 190 ℃ and under a load of 2.16kg is 0.2-30g/10min. Preferably, the L-type polylactic acid and the D-type polylactic acid are compounded, wherein the L-type polylactic acid is 90-95%, the D-type polylactic acid is 5-10%, and the melt flow rate of the polylactic acid is 2-20g/10min (190 ℃ C., 2.16 kg).
4. A high melt strength PLA composite according to any of claims 1 to 3, wherein the carboxyl terminated nitrile rubber is a nitrile rubber powder with carboxyl terminated reactive functional groups at both ends of the molecular chain, and the mooney viscosity is 90 to 140.
5. The high melt strength PLA composite material according to any one of claims 1-4, wherein said bis-aminopropyl polydimethylsiloxane is a polymeric organosilicon compound containing two-NH's at both ends of the molecular chain 2 A radical having a viscosity of 3000 to 10000, preferably 5000 to 10000, at 25 ℃.
6. The high melt strength PLA composite of any of claims 1 to 5, wherein the whiskers are inorganic whiskers including one or more of silicon carbide whiskers, calcium sulfate whiskers, calcium carbonate whiskers, basic magnesium sulfate whiskers, alumina whiskers, potassium titanate whiskers, preferably calcium sulfate whiskers and/or basic magnesium sulfate whiskers, having an aspect ratio >30.
7. The high melt strength PLA composite of any of claims 1-6, wherein the antioxidants include a primary antioxidant and a secondary antioxidant, the primary antioxidant including one or more of a hindered phenol and a hindered amine antioxidant; the auxiliary antioxidant comprises one or more of thioesters and phosphite antioxidants; the primary antioxidant is preferably antioxidant 1010; the secondary antioxidant is preferably an antioxidant 168.
8. The high melt strength PLA composite of any of claims 1-7, wherein the accelerator is one or both of benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate, benzotriazol-1-yloxy tris (dimethylamino) phosphonium hexafluorophosphate.
9. The high melt strength PLA composite of any of claims 1 to 8, wherein the lubricant is one or more of stearic acid, zinc stearate, magnesium stearate.
10. A method of making the high melt strength PLA composite of any of claims 1-9, comprising the steps of:
(1) Putting PLA, carboxyl-terminated nitrile rubber powder, bis-aminopropyl polydimethylsiloxane, whisker, antioxidant, accelerator and lubricant raw materials into a high-speed mixer according to the proportion, and mixing for 10-5min to obtain a uniformly mixed premix;
(2) And adding the premix into a single screw extruder bin, and performing extrusion granulation at 170-200 ℃ to obtain PLA composite material particles with high melt strength.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311589634.0A CN117551340A (en) | 2023-11-27 | 2023-11-27 | PLA composite material with high melt strength and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311589634.0A CN117551340A (en) | 2023-11-27 | 2023-11-27 | PLA composite material with high melt strength and preparation method thereof |
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