CN116444968A - Modified polylactic acid composite film and manufacturing process thereof - Google Patents
Modified polylactic acid composite film and manufacturing process thereof Download PDFInfo
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- CN116444968A CN116444968A CN202310521986.6A CN202310521986A CN116444968A CN 116444968 A CN116444968 A CN 116444968A CN 202310521986 A CN202310521986 A CN 202310521986A CN 116444968 A CN116444968 A CN 116444968A
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- polylactic acid
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- quaternary ammonium
- ammonium salt
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 64
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 37
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 36
- -1 polybutylene adipate terephthalate Polymers 0.000 claims abstract description 26
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims abstract description 15
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000001125 extrusion Methods 0.000 claims description 27
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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 compound 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 5
- 238000002360 preparation method Methods 0.000 claims description 5
- QXZGXRIXJAVMTI-UHFFFAOYSA-N tribenzylsilicon Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)CC1=CC=CC=C1 QXZGXRIXJAVMTI-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005266 casting Methods 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 4
- 229920008262 Thermoplastic starch Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000004628 starch-based polymer Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 3
- OXIKLRTYAYRAOE-CMDGGOBGSA-N (e)-3-(1-benzyl-3-pyridin-3-ylpyrazol-4-yl)prop-2-enoic acid Chemical group N1=C(C=2C=NC=CC=2)C(/C=C/C(=O)O)=CN1CC1=CC=CC=C1 OXIKLRTYAYRAOE-CMDGGOBGSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of films and discloses a modified polylactic acid composite film and a manufacturing process thereof, wherein polylactic acid, polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent, a lubricant and an antioxidant are used as raw materials, and the modified polylactic acid composite film is prepared through granulation, sheet casting and stretching processes.
Description
Technical Field
The invention relates to the technical field of films, in particular to a modified polylactic acid composite film and a manufacturing process thereof.
Background
In today's society with new technological development, plastic film products become one of indispensable polymer plastic products in daily life, and conventional plastic film products often use petroleum-based undegradable polymer materials such as polyethylene, polypropylene and the like as base materials, so that a large amount of plastic film products not only produce ' white pollution ', but also seriously damage the environment, and accelerate the consumption of petroleum resources, and therefore, it is of great importance to find environment-friendly polymer materials to manufacture plastic films. Polylactic acid is a polymer obtained by polymerizing lactic acid serving as a main raw material, has the characteristics of good processability, transparency and the like, and has the characteristic of biodegradability, so that the polylactic acid is an ideal environment-friendly plastic film substrate, but has low glass transition temperature, is easy to decompose in a higher-temperature environment such as a microwave oven and the like, and has basically no antibacterial property, so that the application of the polylactic acid in the fields of food packaging and the like is limited.
The invention patent in China with the application number of CN200710190063.8 discloses a polylactic acid/thermoplastic starch extrusion blow-molded film, a production method and application thereof, wherein polylactic acid, thermoplastic starch, aliphatic-aromatic polyester copolymer and the like are used as raw materials, and the polylactic acid/thermoplastic starch extrusion blow-molded film is prepared into a degradable composite film through extrusion, bracing, water cooling, granulating and blow-molding processes, but the patent does not address the problem of poor heat resistance and antibacterial property of polylactic acid, so that the polylactic acid/thermoplastic starch extrusion blow-molded film has no competitive power in the fields of food packaging and the like in practice.
Disclosure of Invention
The invention aims to provide a modified polylactic acid composite film and a manufacturing process thereof, which solve the problems of poor heat resistance and poor antibacterial property of polylactic acid.
The aim of the invention can be achieved by the following technical scheme:
the modified polylactic acid composite film comprises the following raw materials in parts by weight: 50-60 parts of polylactic acid, 20-30 parts of polybutylene adipate terephthalate, 1-3 parts of organosilicon quaternary ammonium salt antibacterial agent, 1-2 parts of lubricant and 0.5-1 part of antioxidant;
the structural formula of the organosilicon quaternary ammonium salt antibacterial agent is shown as follows:
where z=11, 15,17.
Further, the lubricant is zinc stearate; the antioxidant is any one of antioxidant 168 and antioxidant 1010.
Further, the preparation method of the organosilicon quaternary ammonium salt antibacterial agent comprises the following steps:
the first step: mixing tribenzyl silicon, 1, 3-diglycidyl ether glycerin and toluene, mechanically stirring to form a uniform solution, adding a catalyst into the system, introducing nitrogen for protection, raising the temperature for reaction, evaporating the solvent, taking a solid material, washing, and vacuum drying to obtain an intermediate material;
and a second step of: mixing the intermediate material with tetrahydrofuran, stirring until the intermediate material is completely dissolved, adding dimethyl tertiary amine, uniformly mixing, raising the temperature of the system to 60-65 ℃, stirring for 1-3h, adding glacial acetic acid into the system to regulate the pH of the system, continuously stirring for 4-8h, evaporating the solvent, taking out the solid material, and washing and vacuum drying to obtain the organosilicon quaternary ammonium salt antibacterial agent.
Further, in the first step, the catalyst is trifluoroacetic acid.
Further, in the first step, the temperature of the reaction is 80-100 ℃ and the time is 4-8h.
Further, in the second step, the dimethyl tertiary amine is any one of N, N-dimethyl dodecyl amine, hexadecyl dimethyl tertiary amine or octadecyl dimethyl tertiary amine.
Further, in the second step, the pH value of the regulating system is 6-7.
Through the technical scheme, the tribenzyl silicon structure contains Si-H bond, and under the catalysis of trifluoroacetic acid, the tribenzyl silicon structure can react with active hydroxyl in the 1, 3-diglycidyl ether glycerol structure to obtain an intermediate material containing two equivalents of epoxy groups in the structure, the epoxy groups can perform ring-opening addition reaction with tertiary amine groups in the dimethyl tertiary amine structure to generate active hydroxyl, and meanwhile, quaternary ammonium salt antibacterial groups can be generated to obtain the organosilicon quaternary ammonium salt antibacterial agent.
A manufacturing process of a modified polylactic acid composite film comprises the following steps:
step one: pouring polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent and one half of polylactic acid in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to be 200-220 ℃, and carrying out extrusion granulation to obtain master batch (1);
step two: pouring the lubricant, the antioxidant and the rest half weight of polylactic acid into a stirrer, stirring and mixing uniformly, placing the mixture into a double-screw extruder, setting the extrusion temperature to be 180-200 ℃, and carrying out extrusion granulation to obtain master batch (2);
step three: mixing the master batch (1) and the master batch (2), pouring into a double-screw extruder, extruding and granulating at the temperature of 150-180 ℃, cooling the obtained master batch in the temperature environment of 30-50 ℃, and then placing the cast sheet in the temperature environment of 80-140 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
The invention has the beneficial effects that:
(1) According to the invention, the organosilicon quaternary ammonium salt antibacterial agent is prepared and mixed with the base materials such as polylactic acid, and as the organosilicon quaternary ammonium salt antibacterial agent contains two equivalent hydroxyl groups, the organosilicon quaternary ammonium salt antibacterial agent can serve as a chain extender in the high-temperature extrusion granulation process and is chemically bonded with polylactic acid and polybutylene adipate terephthalate, so that on one hand, the interfacial bonding force between the organosilicon quaternary ammonium salt antibacterial agent and the polylactic acid base materials is improved, on the other hand, the phenomenon that the organosilicon quaternary ammonium salt antibacterial agent is separated out and migrates is effectively avoided, the polylactic acid composite film shows antibacterial durability, on the other hand, the interfacial properties of polylactic acid and polybutylene adipate terephthalate are enhanced, and good interfacial adhesion is generated between the organosilicon quaternary ammonium salt antibacterial agent and the polybutylene adipate terephthalate, so that the toughness of the polylactic acid composite film is enhanced.
(2) The organosilicon quaternary ammonium salt antibacterial agent prepared by the invention contains Si-O bonds with higher bond energy and a large number of rigid benzene rings, and is introduced into a polylactic acid matrix in a chemical connection mode, so that the synergistic effect of the Si-O bonds and the rigid benzene rings can be utilized, and the heat resistance of the polylactic acid composite film can be effectively enhanced. Meanwhile, the addition of the organosilicon quaternary ammonium salt antibacterial agent can enable the polylactic acid composite film to show good antibacterial performance. In addition, the organosilicon quaternary ammonium salt antibacterial agent has strong heat resistance, can not be decomposed in the high-temperature granulation process, and can effectively ensure the antibacterial effect of the antibacterial agent.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of the organosilicon quaternary ammonium salt antibacterial agent in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The modified polylactic acid composite film comprises the following raw materials in parts by weight: 50 parts of polylactic acid, 20 parts of polybutylene adipate terephthalate, 1 part of organosilicon quaternary ammonium salt antibacterial agent, 1 part of zinc stearate and 1680.5 parts of antioxidant;
the manufacturing process of the composite film comprises the following steps:
step one: pouring polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent and one half of polylactic acid in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to be 200 ℃, and carrying out extrusion granulation to obtain master batch (1);
step two: pouring zinc stearate, antioxidant 168 and the rest half weight of polylactic acid into a stirrer, stirring and mixing uniformly, placing into a double-screw extruder, setting the extrusion temperature to 180 ℃, and performing extrusion granulation to obtain master batch (2);
step three: mixing the master batch (1) and the master batch (2), pouring into a double-screw extruder, extruding and granulating at the temperature of 150 ℃, cooling the obtained master batch in the temperature of 30 ℃, and then placing the cast sheet in the temperature of 80 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
The preparation method of the organosilicon quaternary ammonium salt antibacterial agent comprises the following steps:
the first step: mixing 0.5g of tribenzyl silicon, 0.35g of 1, 3-diglycidyl ether glycerol and toluene, mechanically stirring to form a uniform solution, adding 0.05mL of trifluoroacetic acid into the system, introducing nitrogen for protection, raising the temperature to 100 ℃, stirring for 6 hours, evaporating the solvent, taking a solid material, washing, and vacuum drying to obtain an intermediate material;
and a second step of: mixing 0.2g of intermediate material with tetrahydrofuran, stirring until the intermediate material is completely dissolved, adding 0.18g of N, N-dimethyl dodecylamine, uniformly mixing, raising the temperature of the system to 65 ℃, stirring for 2 hours, adding glacial acetic acid into the system, regulating the pH value of the system to 6, continuously stirring for 6 hours, evaporating the solvent, taking out the solid material, and washing and vacuum drying to obtain the organosilicon quaternary ammonium salt antibacterial agent.
The structural formula of the organosilicon quaternary ammonium salt antibacterial agent is shown as follows:
the organosilicon quaternary ammonium salt antibacterial agent is subjected to infrared characterization, the test result is shown in figure 1, and is 3400-3500cm as shown in figure 1 -1 The absorption peak of the hydroxyl is 2800-3000cm -1 The absorption peak of long chain alkyl is 1400-1500cm -1 The absorption peak of C-N in quaternary ammonium salt is 1100-1250cm -1 The absorption peak of ether bond is 1000-1100cm -1 The absorption peak of Si-O bond is 500-850cm -1 The absorption peak of benzene ring is shown.
Example 2
The modified polylactic acid composite film comprises the following raw materials in parts by weight: 55 parts of polylactic acid, 25 parts of polybutylene adipate terephthalate, 2 parts of organosilicon quaternary ammonium salt antibacterial agent, 1.5 parts of zinc stearate and 10100.6 parts of antioxidant;
the manufacturing process of the composite film comprises the following steps:
step one: pouring polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent and one half of polylactic acid in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to 220 ℃, and carrying out extrusion granulation to obtain master batch (1);
step two: pouring zinc stearate, antioxidant 1010 and the rest half weight of polylactic acid into a stirrer, stirring and mixing uniformly, placing into a double-screw extruder, setting the extrusion temperature to be 200 ℃, and carrying out extrusion granulation to obtain master batch (2);
step three: mixing the master batch (1) and the master batch (2), pouring into a double-screw extruder, extruding and granulating at 160 ℃, cooling the obtained master batch in a temperature environment of 40 ℃, and then placing the cast sheet in a temperature environment of 120 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
Wherein the preparation method of the organosilicon quaternary ammonium salt antibacterial agent is the same as that of the example 1.
Example 3
The modified polylactic acid composite film comprises the following raw materials in parts by weight: 60 parts of polylactic acid, 30 parts of polybutylene adipate terephthalate, 3 parts of organosilicon quaternary ammonium salt antibacterial agent, 2 parts of zinc stearate and 1681 parts of antioxidant;
the manufacturing process of the composite film comprises the following steps:
step one: pouring polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent and one half of polylactic acid in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to 220 ℃, and carrying out extrusion granulation to obtain master batch (1);
step two: pouring zinc stearate, antioxidant 168 and the rest half weight of polylactic acid into a stirrer, stirring and mixing uniformly, placing into a double-screw extruder, setting the extrusion temperature to be 200 ℃, and carrying out extrusion granulation to obtain master batch (2);
step three: mixing the master batch (1) and the master batch (2), pouring into a double-screw extruder, extruding and granulating at the temperature of 180 ℃, cooling the obtained master batch in the temperature of 50 ℃, and then placing the cast sheet in the temperature of 140 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
Wherein the preparation method of the organosilicon quaternary ammonium salt antibacterial agent is the same as that of the example 1.
Comparative example 1
The modified polylactic acid composite film comprises the following raw materials in parts by weight: 55 parts of polylactic acid, 25 parts of polybutylene adipate terephthalate, 1.5 parts of zinc stearate and 0.6 part of antioxidant 1010;
the manufacturing process of the composite film specifically comprises the following steps:
and pouring the polylactic acid, the polybutylene terephthalate, the zinc stearate and the antioxidant 1010 in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to 220 ℃, carrying out extrusion granulation, cooling the obtained master batch into cast sheets in a temperature environment of 40 ℃, and then placing the cast sheets in a temperature environment of 120 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
Performance detection
Cutting the composite films prepared in the examples 1-3 and the comparative example 1 into test samples meeting the specification, and selecting escherichia coli as a test strain according to the standard GB/T31402-2015 to test the bacteriostasis rate of the samples; testing the mechanical properties of a sample according to the reference standard GB/T1040.3-2006; the samples were tested for glass transition temperature using differential scanning calorimetry and the test results are given in the following table:
| example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Bacteriostatic rate/% | >99 | >99 | >99 | <52 |
| Tensile Strength/MPa | 45.9 | 46.4 | 46.0 | 34.6 |
| Elongation at break/% | 5.2 | 5.6 | 5.5 | 3.4 |
| Glass transition temperature/DEGC | 69.3 | 70.0 | 69.6 | 64.2 |
As can be seen from the above table, the composite film prepared in the examples 1-3 of the present invention has good antibacterial property, mechanical property and heat resistance, while the composite film prepared in the comparative example 1 cannot enhance the interfacial properties of polylactic acid and polybutylene terephthalate adipate due to the fact that the organosilicon quaternary ammonium salt antibacterial agent is not added, and cannot introduce a rigid benzene ring and Si-O bond with high bond energy into the polylactic acid matrix, so that each performance is poor.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. The modified polylactic acid composite film is characterized by comprising the following raw materials in parts by weight: 50-60 parts of polylactic acid, 20-30 parts of polybutylene adipate terephthalate, 1-3 parts of organosilicon quaternary ammonium salt antibacterial agent, 1-2 parts of lubricant and 0.5-1 part of antioxidant;
the structural formula of the organosilicon quaternary ammonium salt antibacterial agent is shown as follows:
where z=11, 15,17.
2. The modified polylactic acid composite film according to claim 1, wherein said lubricant is zinc stearate; the antioxidant is any one of antioxidant 168 and antioxidant 1010.
3. The modified polylactic acid composite film according to claim 1, wherein the preparation method of the organosilicon quaternary ammonium salt antibacterial agent comprises the following steps:
the first step: mixing tribenzyl silicon, 1, 3-diglycidyl ether glycerin and toluene, mechanically stirring to form a uniform solution, adding a catalyst into the system, introducing nitrogen for protection, raising the temperature for reaction, evaporating the solvent, taking a solid material, washing, and vacuum drying to obtain an intermediate material;
and a second step of: mixing the intermediate material with tetrahydrofuran, stirring until the intermediate material is completely dissolved, adding dimethyl tertiary amine, uniformly mixing, raising the temperature of the system to 60-65 ℃, stirring for 1-3h, adding glacial acetic acid into the system to regulate the pH of the system, continuously stirring for 4-8h, evaporating the solvent, taking out the solid material, and washing and vacuum drying to obtain the organosilicon quaternary ammonium salt antibacterial agent.
4. A modified polylactic acid composite film according to claim 3, wherein in the first step, said catalyst is trifluoroacetic acid.
5. A modified polylactic acid composite film according to claim 3, wherein in the first step, the reaction temperature is 80 to 100 ℃ for 4 to 8 hours.
6. A modified polylactic acid composite film according to claim 3, wherein in the second step, said dimethyl tertiary amine is any one of N, N-dimethyldodecylamine, hexadecyldimethyl tertiary amine or octadecyl dimethyl tertiary amine.
7. A modified polylactic acid composite film according to claim 3, wherein in the second step, the pH of the system is adjusted to 6 to 7.
8. A process for producing the modified polylactic acid composite film according to claim 1, comprising the steps of:
step one: pouring polybutylene adipate terephthalate, an organosilicon quaternary ammonium salt antibacterial agent and one half of polylactic acid in parts by weight into a stirrer, stirring and mixing uniformly, transferring into a double-screw extruder, setting the extrusion temperature to be 200-220 ℃, and carrying out extrusion granulation to obtain master batch (1);
step two: pouring the lubricant, the antioxidant and the rest half weight of polylactic acid into a stirrer, stirring and mixing uniformly, placing the mixture into a double-screw extruder, setting the extrusion temperature to be 180-200 ℃, and carrying out extrusion granulation to obtain master batch (2);
step three: mixing the master batch (1) and the master batch (2), pouring into a double-screw extruder, extruding and granulating at the temperature of 150-180 ℃, cooling the obtained master batch in the temperature environment of 30-50 ℃, and then placing the cast sheet in the temperature environment of 80-140 ℃ for asynchronous biaxial stretching to obtain the polylactic acid composite film.
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