CN114350127B - Degradable antibacterial functional master batch special for polylactic acid and preparation method thereof - Google Patents
Degradable antibacterial functional master batch special for polylactic acid and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 67
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 59
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 59
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 29
- 230000032683 aging Effects 0.000 claims abstract description 25
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 claims abstract description 19
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 31
- 238000001125 extrusion Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 10
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 15
- 239000004033 plastic Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 11
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 10
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
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- 108091007643 Phosphate carriers Proteins 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
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- 238000011056 performance test Methods 0.000 description 2
- -1 polybutylene terephthalate Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of plastic modification processing, in particular to a special degradable antibacterial functional master batch for polylactic acid and a preparation method thereof, wherein the antibacterial functional master batch comprises the following components in percentage by mass: 75.0 to 85.0wt.% of low molecular weight polylactic acid; 10.0 to 20.0wt.% of an inorganic antibacterial agent; 1.0 to 3.0wt.% of nano cerium dioxide; 1.0 to 3.0wt.% of mesoporous zirconium hydrogen phosphate; 0.1 to 0.3wt.% of a thermo-oxidative aging resistant aid; 2.5 to 3.0wt.% of dispersing aid. According to the antibacterial functional master batch provided by the invention, the powder antibacterial agent of the silver-zinc ion inorganic carrier is adopted, and the mesoporous zirconium hydrogen phosphate is introduced into the antibacterial functional master batch, so that the antibacterial performance of the special modified polylactic acid material adopting the antibacterial functional master batch can be obviously improved, the action period of the antibacterial function of the modified biodegradable plastic can be prolonged, and the processing efficiency can be improved.
Description
Technical Field
The invention relates to the technical field of plastic modification processing, in particular to a degradable antibacterial functional master batch special for polylactic acid and a preparation method thereof.
Background
The method for modifying the thermoplastic plastics by adopting the double-screw extrusion granulator set to carry out melt blending is a simple and easy traditional thermoplastic plastics modification method, has excellent modification effect, can realize continuous production of plastic modified products, and the prepared modified special material can be processed into various plastic products by injection or extrusion. The technical route can not only improve the physical and mechanical properties of the plastic product such as strength, toughness, rigidity, creep resistance, flex resistance and the like, but also endow the plastic product with special physical and chemical properties such as flame retardance, electric conduction, heat conduction, magnetic conduction, static resistance, antibiosis and the like. At present, the development of plastic masterbatch technology is rapidly developed, the preparation technology of plastic masterbatch is continuously optimized, and the functional varieties are more and more.
The biodegradable plastic has good degradability, is a plastic material with sustainable development, and is widely applied to the fields of food soft and hard packaging materials and disposable quick-release materials. Polylactic acid is used as a main product in biodegradable plastics, and the requirements of the market on the antibacterial property of the polylactic acid are also increasingly strict. The patent CN201811565072.5 discloses a special antibacterial master batch for biodegradable garbage bags and a preparation method thereof, wherein the master batch is prepared by taking polybutylene terephthalate and polylactic acid as carrier resins, taking papermaking waste as an antibacterial auxiliary agent, and carrying out melt blending extrusion by a double-screw pull-out granulator set. Patent CN202120866353.5 discloses a nano composite plastic antibacterial master batch, which is modified by constructing a main antibacterial master batch main body and a protective layer.
However, in the plastic blending modification processing process, the blending processing of the granular resin and the powder or the liquid modification auxiliary agent has the problems of complex batching process, uneven raw material dispersion, environmental pollution caused by dust emission and the like, and further the antibacterial performance of the product can be influenced. In the field of plastic processing industry, melt blending processing by adopting corresponding functionalized modified plastic master batches is one of methods for overcoming the problems.
Disclosure of Invention
The invention aims to provide a special degradable antibacterial function master batch for polylactic acid and a preparation method thereof, which are used for solving the problems in the background art.
The invention is realized by the following technical scheme:
the special degradable antibacterial master batch for polylactic acid comprises the following components in percentage by mass:
low molecular weight polylactic acid: 75.0 to 85.0wt.%;
inorganic antibacterial agent: 10.0 to 20.0wt.%;
nano cerium oxide: 1.0 to 3.0wt.%;
mesoporous zirconium hydrogen phosphate: 1.0 to 3.0wt.%;
thermal-oxidative aging resistance auxiliary agent: 0.1 to 0.3wt.%;
dispersing auxiliary agent: 2.5 to 3.0wt.%.
Preferably, the number average molecular weight of the low molecular weight polylactic acid is 8000-12000 g/mol.
Preferably, the inorganic antibacterial agent is silver zinc ion inorganic powder antibacterial agent.
Preferably, the inorganic antibacterial agent is selected from any one of silver and zinc ion inorganic powder antibacterial agents taking glass, zeolite or phosphate as a carrier.
Preferably, the particle size of the inorganic antibacterial agent is 5 to 10 microns.
Preferably, the anti-thermo-oxidative aging auxiliary agent is a compound of triethylene glycol bis beta- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant 245) and bis (2, 4-di-tertiary butyl phenyl) pentaerythritol diphosphite (antioxidant 626).
Preferably, the mass ratio of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate to bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite in the compound includes, but is not limited to, 1:1.
preferably, the dispersing agent is selected from any one or two of calcium stearate, zinc stearate, oleamide and mesoporous acid amide.
The invention also provides a preparation method of the degradable antibacterial function master batch special for polylactic acid, which specifically comprises the following steps: weighing low molecular weight polylactic acid, inorganic antibacterial agent, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent and dispersing auxiliary agent according to the proportion, and sequentially adding the components into a high-speed mixer for premixing to obtain premix; and adding the premix into a double-screw extrusion granulator set through a conical feeder, and carrying out melt extrusion and granulation to obtain the master batch with the target antibacterial function.
As a further scheme of the invention, the temperature of each section from the feed cylinder of the double-screw extrusion granulator to the machine head is 135-175 ℃, and the rotating speed of the screw is 300-400 rpm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention designs the low molecular weight polylactic acid master batch carrier which has excellent flow dispersibility, self biodegradability and complete compatibility with the polylactic acid matrix aiming at the molecular structural characteristics of the polylactic acid matrix raw material, so that each component in the antibacterial master batch can keep good compatibility with the polylactic acid matrix, the dispersibility of the powder raw material in the matrix is improved, and the mechanical property can be effectively maintained.
2. According to the invention, the powder antibacterial agent of the silver-zinc ion inorganic carrier and the nano compound are compounded for use, so that the antibacterial performance of the special modified polylactic acid material adopting the antibacterial function master batch can be remarkably improved.
3. According to the invention, mesoporous zirconium hydrogen phosphate is introduced into the antibacterial function master batch, so that free silver, zinc and cerium ions can be adsorbed, the excessively rapid failure of the antibacterial function due to ion migration is prevented, the action period of the antibacterial function of the modified biodegradable plastic is prolonged, the effect of the efficient nucleating agent is exerted, the crystallization rate of the biodegradable plastic is improved, the processing and forming period of the biodegradable plastic is shortened, and the processing efficiency is improved.
4. The degradable antibacterial master batch provided by the invention can be used for preparing a special modified material by melt blending with other modified auxiliary agents and polylactic acid matrix resin through a double-screw granulator, or can be directly processed into a product by injection molding of an injection molding machine after being simply mixed with the polylactic acid matrix, can be flexibly combined with other modified master batches and auxiliary agents, can be flexibly adjusted in proportion with the polylactic acid resin raw materials to adjust the performance and cost of a plastic product, and can be widely applied to antibacterial functional modification and processing of various polylactic acid plastic products.
Detailed Description
The invention is further illustrated below with reference to examples. The preferred embodiments do not describe all details in detail nor limit the invention to the specific embodiments described. Unless otherwise specified, the methods in the examples are all routine methods of experiments, and the experimental materials used are readily available from commercial companies.
The low molecular weight polylactic acid used in examples 1 to 6 and comparative examples 1 to 6 had a number average molecular weight of 8000 to 12000g/mol and the inorganic antibacterial agent had a particle diameter of 5 to 10. Mu.m.
Example 1:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 85.0kg of low molecular weight polylactic acid; 10.0kg of silver zinc ion antibacterial agent (Bactekiller BM-102 TG) of glass/zeolite carrier; 3.0kg of nano cerium oxide; 1.0kg of mesoporous zirconium hydrogen phosphate; 0.1kg of a thermo-oxidative aging resistant auxiliary agent; 2.9kg of calcium stearate. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver-zinc ion antibacterial agent of glass/zeolite carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent and calcium stearate according to the proportion, and sequentially adding the components into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, the temperature of each section of a feed cylinder of the double-screw extruder to a machine head is 135, 165, 170, 175 and 170 ℃, the screw rotation speed is 350 revolutions per minute, and the blend is melted, extruded and granulated to obtain the target antibacterial function master batch.
Example 2:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 75.0kg of low molecular weight polylactic acid; 18.0kg of silver ion antibacterial agent (Bactekiller BM-502 FA) of glass carrier; 1.0kg of nano cerium oxide; 3.0kg of mesoporous zirconium hydrogen phosphate; 0.3kg of a thermo-oxidative aging resistant auxiliary agent; 2.7kg of zinc stearate. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver ion antibacterial agent of glass carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent and zinc stearate according to the proportion, and sequentially adding the components into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, a feed cylinder of the double-screw extruder is arranged until the temperatures of all sections of a machine head are 138, 165, 170, 175, 170 and 170 ℃, the rotating speed of a screw is 320 revolutions per minute, and the blend is melted, extruded and granulated to obtain the master batch with the target antibacterial function.
Example 3:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 82.0kg of low molecular weight polylactic acid; 13.0kg of silver zinc ion antibacterial agent (Bactekiller BM-102 SD) of glass/zeolite carrier; 3.0kg of nano cerium oxide; 1.0kg of mesoporous zirconium hydrogen phosphate; 0.2kg of a thermo-oxidative aging resistant auxiliary agent; 2.8kg of oleamide. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver-zinc ion antibacterial agent of glass/zeolite carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent and oleamide according to the proportion, and sequentially putting the components into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, the temperature of each section of a feed cylinder of the double-screw extruder to a machine head is 135, 165, 170, 175 and 170 ℃, the screw rotation speed is 350 revolutions per minute, and the blend is melted, extruded and granulated to obtain the target antibacterial function master batch.
Example 4:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 75.0kg of low molecular weight polylactic acid; 20.0kg of phosphate carrier silver ion antibacterial agent (Bactekiller BM-102SVP 01); 1.0kg of nano cerium oxide; 2.0kg of mesoporous zirconium hydrogen phosphate; 0.2kg of a thermo-oxidative aging resistant auxiliary agent; 1.0kg of oleamide and 0.8kg of mesogenic amide. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver ion antibacterial agent (Bactekiller BM-102SVP 01) of phosphate carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, anti-thermo-oxidative aging auxiliary agent, oleamide and mesoporous amide according to the proportion, and sequentially adding the materials into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, the temperature of each section of a feed cylinder of the double-screw extruder to a machine head is 138, 165, 175, 170 and 170 ℃, the screw rotating speed is 400 revolutions per minute, and the blend is melted, extruded and granulated to obtain the target antibacterial function master batch.
Example 5:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 75.0kg of low molecular weight polylactic acid; 20.0kg of phosphate carrier silver ion antibacterial agent (Bactekiller BM-102SVP 02); 1.0kg of nano cerium oxide; 2.0kg of mesoporous zirconium hydrogen phosphate; 0.2kg of a thermo-oxidative aging resistant auxiliary agent; 1.0kg of oleamide and 0.8kg of mesogenic amide. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver ion antibacterial agent (Bactekiller BM-102SVP 02) of phosphate carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, anti-thermo-oxidative aging auxiliary agent, oleamide and mesoporous amide according to the proportion, and sequentially adding the materials into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, the temperature of each section of a feed cylinder of the double-screw extruder to a machine head is 138, 165, 175, 170 and 170 ℃, the screw rotating speed is 400 revolutions per minute, and the blend is melted, extruded and granulated to obtain the target antibacterial function master batch.
Example 6:
the embodiment provides a special degradable antibacterial function master batch for polylactic acid, which comprises the following components in parts by mass: 80.0kg of low molecular weight polylactic acid; 13.0kg of silver zinc ion antibacterial agent (Bactekiller BM-102 TG) of glass/zeolite carrier; 2.0kg of nano cerium oxide; 2.8kg of mesoporous zirconium hydrogen phosphate; 0.2kg of a thermo-oxidative aging resistant auxiliary agent; 1.0kg of oleamide and 1.0kg of mesogenic amide. Wherein, the anti-thermo-oxidative aging auxiliary agent is a compound formed by an antioxidant 245 and an antioxidant 626 according to a mass ratio of 1:1.
The embodiment also provides a preparation method of the antibacterial function master batch, which specifically comprises the following steps:
weighing low molecular weight polylactic acid, silver zinc ion antibacterial agent of glass/zeolite carrier, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent, oleamide and mesoporous amide according to the proportion, and sequentially adding the components into a high-speed mixer for premixing to obtain premix; the premix is added into a double-screw extrusion granulator set through a conical feeder, a feed cylinder of the double-screw extruder is arranged until the temperatures of all sections of a machine head are 137, 167, 172, 174, 175, 171 and 170 ℃, the rotating speed of a screw is 360 revolutions per minute, and the blend is melted, extruded and granulated to obtain the master batch with the target antibacterial function.
The preparation method of examples 1-6 is used for preparing corresponding special degradable antibacterial function master batches for polylactic acid, and the antibacterial function master batches prepared in examples 1-6 are mixed with polylactic acid resin, wherein the mass percentages of the antibacterial function master batches are 15 wt%, the antibacterial function master batches are blended and extruded into materials through a double-screw extruder, and the materials are injection molded through an injection molding machine, so that the sample bars for mechanical property test of examples 1-6 are obtained.
Meanwhile, according to the raw material formulas and compositions of examples 1-6, only polylactic acid raw materials are mixed with the Fuji chemical antibacterial agents with the same content and the same brand, and the polylactic acid raw materials are directly pulled out of a granulator set through double screws to be melt, blended and granulated according to the corresponding preparation method under the same processing conditions, and the comparative examples 1-6 are obtained through injection molding.
In order to verify the modification effect of the degradable antibacterial function master batch prepared by the invention on polylactic acid, performance tests are carried out on examples 1-6 and comparative examples 1-6, namely, tensile performance is tested according to national standard GB/T1040, cantilever beam impact performance is tested according to national standard GB/T1843, and antibacterial performance of the product surface is tested according to national standard GB/T31402.
The performance test data for examples 1-6 and comparative examples 1-6 are shown in Table 1.
Table 1:
as shown by the test results in Table 1, compared with comparative examples 1-6, the antibacterial rates of the biodegradable plastics prepared in examples 1-6 of the present invention on coliform bacteria and staphylococcus aureus are higher than those of the corresponding comparative examples, and all the antibacterial functional master batches meet the complete antibacterial standard of national standard GB/T31402, which shows that the antibacterial functional master batches provided by the present invention have more excellent antibacterial performance, and only comparative examples 4 and 5 in comparative examples 1-6 meet the complete antibacterial standard of national standard GB/T31402. In addition, the impact resistance and the tensile strength of the special biodegradable plastic modified composite for polylactic acid prepared by the embodiment 1-6 are better than those of the biodegradable plastic modified composite modified by direct blending, so that the antibacterial functional master batch of the biodegradable plastic disclosed by the invention can effectively improve the mechanical property of the modified product.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments do not describe all details in detail nor limit the invention to the specific embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The special degradable antibacterial master batch for polylactic acid is characterized by comprising the following components in percentage by mass:
low molecular weight polylactic acid: 75.0 to 85.0wt.%;
inorganic antibacterial agent: 10.0 to 20.0wt.%;
nano cerium oxide: 1.0 to 3.0wt.%;
mesoporous zirconium hydrogen phosphate: 1.0 to 3.0wt.%;
thermal-oxidative aging resistance auxiliary agent: 0.1 to 0.3wt.%;
dispersing auxiliary agent: 2.5 to 3.0wt.%;
the number average molecular weight of the low molecular weight polylactic acid is 8000-12000 g/mol;
the inorganic antibacterial agent is selected from any one of silver and zinc ion inorganic powder antibacterial agents taking glass, zeolite or phosphate as carriers.
2. The special degradable antibacterial functional master batch for polylactic acid according to claim 1, wherein the particle size of the inorganic antibacterial agent is 5-10 microns.
3. The special degradable antibacterial functional master batch for polylactic acid according to claim 1, wherein the thermo-oxidative aging resistant additive is a compound of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
4. The special degradable antibacterial function master batch for polylactic acid according to claim 3, wherein the mass ratio of triethylene glycol bis beta- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate to bis (2, 4-di-tertiary butylphenyl) pentaerythritol diphosphite in the compound comprises, but is not limited to, 1:1.
5. the special degradable antibacterial functional master batch for polylactic acid according to claim 1, wherein the dispersing agent is any one or two of calcium stearate, zinc stearate, oleamide and mesoporous acid amide.
6. A method for preparing the special degradable antibacterial function master batch for polylactic acid according to any one of claims 1 to 5, which is characterized by comprising the following steps:
weighing low molecular weight polylactic acid, inorganic antibacterial agent, nano cerium dioxide, mesoporous zirconium hydrogen phosphate, thermo-oxidative aging resistant auxiliary agent and dispersing auxiliary agent according to the proportion, and sequentially adding the components into a high-speed mixer for premixing to obtain premix; and adding the premix into a double-screw extrusion granulator set through a conical feeder, and carrying out melt extrusion and granulation to obtain the master batch with the target antibacterial function.
7. The method for preparing the special degradable antibacterial master batch for polylactic acid, which is disclosed in claim 6, wherein the temperature from the charging barrel of the double-screw extrusion granulator to each section of the machine head is 135-175 ℃, and the screw rotation speed is 300-400 rpm.
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