CN115559150A - Antibacterial degradable paper-plastic composite coating film layer material and preparation method thereof - Google Patents
Antibacterial degradable paper-plastic composite coating film layer material and preparation method thereof Download PDFInfo
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- CN115559150A CN115559150A CN202111639311.9A CN202111639311A CN115559150A CN 115559150 A CN115559150 A CN 115559150A CN 202111639311 A CN202111639311 A CN 202111639311A CN 115559150 A CN115559150 A CN 115559150A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 100
- 239000004033 plastic Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 title description 6
- 238000000576 coating method Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000011858 nanopowder Substances 0.000 claims abstract description 23
- 239000003208 petroleum Substances 0.000 claims abstract description 21
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 19
- 239000003242 anti bacterial agent Substances 0.000 claims description 47
- 239000002667 nucleating agent Substances 0.000 claims description 45
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 45
- -1 polybutylene succinate Polymers 0.000 claims description 42
- 239000004626 polylactic acid Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000004593 Epoxy Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 239000004631 polybutylene succinate Substances 0.000 claims description 2
- 229920002961 polybutylene succinate Polymers 0.000 claims description 2
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 239000000600 sorbitol Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 9
- 241000700605 Viruses Species 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 4
- 238000004332 deodorization Methods 0.000 abstract description 3
- 231100000344 non-irritating Toxicity 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 241000588724 Escherichia coli Species 0.000 abstract description 2
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 32
- 239000003963 antioxidant agent Substances 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 17
- 238000010030 laminating Methods 0.000 description 16
- 239000004611 light stabiliser Substances 0.000 description 16
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 16
- 230000003078 antioxidant effect Effects 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 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 description 11
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000004790 ingeo Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of C08L101/16, in particular to an antibacterial degradable paper-plastic composite spray film layer material and a preparation method thereof, wherein the antibacterial degradable paper-plastic composite spray film layer material is prepared from 70-98 parts of bio-based plastic, 0.5-30 parts of petroleum-based plastic, 0.6-10 parts of inorganic nano powder, 0.1-1 part of functional compound and 0.1-5 parts of processing aid, and has good processing performance, so that the provided paper-plastic composite spray film layer material can efficiently and rapidly kill various virus bacteria, realizes long-acting sterilization and long-acting deodorization, is harmless and nonirritating to human bodies and environments, has the antibacterial rate of 99.99% to escherichia coli and staphylococcus aureus, has outstanding tear resistance, tensile property and transparent property, and is particularly suitable for the field of cold chain transportation industry.
Description
Technical Field
The invention relates to the field of C08L101/16, in particular to an antibacterial degradable paper-plastic composite laminated film layer material and a preparation method thereof.
Background
The development of society and the progress of science and technology make people have higher and higher requirements on living environment, people have stronger and stronger environmental awareness, particularly in the fields of catering industry and cold chain transportation industry, in view of sanitary safety, a large number of disposable articles are used in the fields of catering industry and cold chain transportation industry, the consumption of paper-plastic materials including disposable paper cups, paper trays, paper holders, cup holders, paper boxes and the like is huge, but most of the paper-plastic materials used in the current market can not be effectively degraded and recycled, mainly because the polyethylene or polypropylene material is used as a coating layer of the paper-plastic materials in the prior art, chinese patent CN108716158B discloses degradable food paper and a preparation method thereof, the coating layer of the degradable food paper takes polyethylene as a main raw material, the leaching film layer of the degradable food paper is prepared under the existence of a photocatalyst, a fiber auxiliary agent, an anchoring agent, a stripping agent and an ultraviolet absorbent, although the paper forming strength and the using effect of the food paper are improved to a certain degree, effective degradation cannot be realized, which inevitably causes a large amount of paper-plastic pollution, in addition, with the further discovery of the transmission path of new coronavirus, part of virus can survive and breed in the cold chain transportation process, and the quality of the cold chain product and the human health are seriously threatened, so how to provide the antibacterial degradable paper-plastic composite leaching film layer material to simultaneously solve the important problem about the livelihood of people in the existing paper-plastic pollution and the survival and breeding problems of the virus and the germ in the cold chain transportation industry.
Disclosure of Invention
In order to solve the problems, the invention provides an antibacterial degradable paper-plastic composite coating film layer material which at least comprises the following raw materials in parts by weight: 70 to 98 portions of bio-based plastic, 0.5 to 30 portions of petroleum-based plastic, 0.6 to 10 portions of inorganic nano powder, 0.1 to 1 portion of functional compound and 0.1 to 5 portions of processing aid.
As a preferable technical scheme, the bio-based plastic is selected from at least one of polyhydroxyalkanoate, polylactic acid and polyamino acid; preferably, the bio-based plastic is polylactic acid; preferably, the weight average molecular weight of the polylactic acid is 2 to 25 ten thousand, and preferably, the polylactic acid is selected from at least one of polylactic acid Ingeo 4032D, PDLA3.4 ten thousand and PDLA6 ten thousand; in the research process, the polylactic acid Ingeo 4032D with the weight-average molecular weight of 20 ten thousand is adopted to realize stable and effective combination with inorganic nano powder in a system, so that the prepared paper-plastic composite coating film layer material has outstanding degradation performance and excellent antibacterial performance, transparency and tensile property.
The supplier of the polylactic acid Ingeo 4032D is NatureWorks.
As a preferable technical scheme, the petroleum-based plastic is selected from one or a combination of more of polycaprolactone, polybutylene succinate, polybutylene adipate-terephthalate and a polybutylene succinate-adipate copolymer; preferably, the petroleum-based plastic is poly (butylene adipate-terephthalate), the degradability of the material of the paper-plastic composite laminated film layer is effectively improved, meanwhile, the toughening effect on polylactic acid is realized, and the tearing performance of the material of the paper-plastic composite laminated film layer is improved.
The polybutylene adipate-terephthalate is named as Ecoworld, purchased from Jinhui Huilong Highnew technology GmbH.
As a preferred technical scheme, the inorganic nano powder at least comprises an antibacterial agent and a nucleating agent; preferably, the mass ratio of the antibacterial agent to the nucleating agent is (0.5-5): (0.1-5), the antibacterial property of the paper-plastic composite laminating layer material is obviously improved, and the physical and mechanical properties of the material are obviously improved.
As a preferable technical scheme, the antibacterial agent is one or a mixture of a plurality of metal ion antibacterial agents, photocatalytic antibacterial agents and metal oxide antibacterial agents. Preferably, the antibacterial agent is a metal ion antibacterial agent or a metal oxide antibacterial agent, preferably, the antibacterial agent is a metal oxide antibacterial agent, further preferably, the metal oxide antibacterial agent is at least one selected from nano zinc oxide, nano titanium dioxide and nano calcium oxide, and preferably, the antibacterial agent is nano zinc oxide. According to the application, the metal ion antibacterial agent or the metal oxide antibacterial agent is adopted, and particularly the metal oxide antibacterial agent nano zinc oxide is introduced, so that the provided paper-plastic composite laminating layer material can efficiently and quickly kill various viruses and bacteria, long-acting sterilization and long-acting deodorization are realized, the paper-plastic composite laminating layer material is harmless and nonirritating to human bodies and the environment, and the problem of virus and germ survival in the transportation process in the cold chain transportation industry is solved; meanwhile, the nucleating agent and the polybutylene adipate-terephthalate in the synergistic system increase the crystallization density of the polylactic acid, promote the grain size to be micronized, shorten the molding period, improve the processing efficiency, obviously improve the transparency, the surface gloss and the tensile strength of the paper-plastic composite laminating layer material, and are particularly suitable for the field of cold chain transportation industry.
The product number of the nano zinc oxide is HSL-PA-3702, and the nano zinc oxide is purchased from Zhongxing nano material Co.
According to the application, the antibacterial degradable paper-plastic composite laminating layer material is provided by adopting the plastic polylactic acid as a bio-based plastic and matching with the petroleum-based plastic polybutylene adipate-terephthalate, but the polylactic acid and the polybutylene adipate-terephthalate have slow crystallization rate and low crystallinity, and the incomplete crystallization causes unstable performance of the product due to environmental influence. Preferably, the nucleating agent is an oxide nucleating agent; the oxide nucleating agent is an oxide nucleating agent RQT-CH, and the crystallization rate and the crystallinity of polylactic acid and polybutylene adipate-terephthalate in the processing process are obviously improved by adopting the oxide nucleating agent RQT-CH in the application, so that the crystal spherulites are micronized, the transparency, the toughness and the strength of the paper-plastic composite laminated film layer material are improved, the adhesion effect of the polylactic acid and the polybutylene adipate-terephthalate in the processing process is reduced, and the process stability and the product size stability are improved.
The oxide nucleating agent RQT-CH was purchased from Henan Ruiqi speciality Chemicals, inc.
In addition, the applicant finds that the degradation and performance degradation of the film layer material may occur in the process of actually processing and producing the paper-plastic composite laminated film layer material, and the analysis reason may be as follows: the polylactic acid and the polybutylene adipate-terephthalate in the system contain ester groups with low stability, and are easy to thermally degrade and hydrolyze under the conditions of moist heat and shearing, so that the molecular weight of the polylactic acid and the polybutylene adipate-terephthalate is reduced, the number of terminal carboxyl groups is increased, and the high-concentration terminal carboxyl groups can further promote the degradation of the polylactic acid and the polybutylene adipate-terephthalate, thereby causing the uncontrollable degradation of materials and the degradation of mechanical and chemical properties. As a preferable technical scheme, the functional compound is one or a mixture of more of alcohol compounds, amine compounds, methacrylate compounds and epoxy compounds. Preferably, the functional compound is a methacrylate compound, and preferably, the melt flow rate (190 ℃,2.16 kg) of the methacrylate compound is 25-45g/10min; preferably, the methacrylate compound is a styrene-methacrylate copolymer, and the end capping is carried out on the polyester end group with high efficiency, so that the effects of inhibiting degradation, extending chain and increasing viscosity are achieved, the uncontrollable degradation behavior caused by the active end group is prevented, the melt strength and viscosity are increased, the dispersibility of the inorganic nano powder material in the polylactic acid and the poly adipic acid-butylene terephthalate is improved, and the product quality of the paper-plastic composite laminating layer material is ensured.
The styrene-methacrylate copolymer was model number SG-20, purchased from Kunststoff-Kogyo Co., ltd.
As a preferable technical scheme, the processing aid is one or a mixture of more than one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, thioester antioxidants, salicylate ultraviolet absorbers, benzophenone ultraviolet absorbers, hindered amine light stabilizers and benzotriazole ultraviolet absorbers. Preferably, the processing aid is a combination of a phosphite antioxidant and a hindered amine light stabilizer, and preferably, the mass ratio of the phosphite antioxidant to the hindered amine light stabilizer is (0.8-1.2): (0.5-1.5); preferably, the phosphite antioxidant is antioxidant-1010, and the hindered amine light stabilizer is UV-770. The mass ratio of (0.8-1.2): (0.5-1.5) antioxidant-1010 and UV-770, absorb the ultraviolet ray in the sunlight effectively, can prevent the material from aging of heat oxygen in processing or using, improve the weathering resistance of the compound laminating film material of paper plastic effectively, lengthen the service life of the compound laminating film material of paper plastic.
The antioxidant-1010 and UV-770 were both purchased from BASF corporation, germany.
The invention also provides a preparation method of the antibacterial degradable paper-plastic composite laminating layer material, which at least comprises the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 5-20 min by adopting a high-speed mixer under the condition that the rotating speed is 300-1500 rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the composite material.
The temperature of the double-screw extruder in the step (2) is 170-220 ℃, the rotating speed is 250-500 rpm, and the ratio of the length to the diameter of the screw is (36-52): 1.
has the beneficial effects that:
1. the invention provides an antibacterial degradable paper-plastic composite laminated film layer material, which has the antibacterial rate of 99.99 percent on escherichia coli and staphylococcus aureus, has outstanding tear resistance, tensile property and transparency, and is particularly suitable for the field of cold chain transportation industry.
2. The poly (butylene adipate-terephthalate) with the weight-average molecular weight of 2000-50000 is adopted, so that the degradability of the paper-plastic composite laminating layer material is effectively improved, the poly (lactic acid) is toughened, the tearing performance of the paper-plastic composite laminating layer material is improved, the crystallization behavior of the poly (lactic acid) can be promoted to a certain extent, and the crystallization rate of the poly (lactic acid) is remarkably improved by cooperating with inorganic nano powder in a system, so that the transparency and the tensile property of the paper-plastic composite laminating layer material are improved.
3. According to the application, the metal ion antibacterial agent or the metal oxide antibacterial agent is adopted, and particularly the metal oxide antibacterial agent nano zinc oxide is introduced, so that the provided paper-plastic composite laminating layer material can efficiently and quickly kill various viruses and bacteria, long-acting sterilization and long-acting deodorization are realized, the paper-plastic composite laminating layer material is harmless and nonirritating to human bodies and the environment, and the problem of virus and bacteria survival in the transportation process in the cold chain transportation industry is solved; meanwhile, the nucleating agent and the poly (butylene adipate-terephthalate) in the synergistic system increase the crystallization density of the polylactic acid, promote the grain size to be micronized, shorten the forming period, improve the processing efficiency, obviously improve the transparency, the surface gloss and the tensile strength of the paper-plastic composite laminating layer material, and are particularly suitable for the field of cold chain transportation industry.
4. In the application, the crystallization rate and the crystallinity of polylactic acid and polybutylene adipate-terephthalate in the processing process are obviously improved by adopting the oxide nucleating agent RQT-CH, so that the crystal spherulites are micronized, the transparency, the toughness and the strength of the paper-plastic composite laminated film layer material are improved, the adhesion effect of the polylactic acid and the polybutylene adipate-terephthalate in the processing process is reduced, and the process stability and the product size stability are improved.
5. By adopting the methacrylate compound as the styrene-methacrylate copolymer, the end capping is carried out on the polyester end group with high efficiency, the effects of inhibiting degradation, chain extension and tackifying are achieved, the uncontrollable degradation behavior caused by the active end group is prevented, the melt strength and viscosity are increased, the dispersibility of the inorganic nano powder material in the polylactic acid and the poly (butylene adipate-terephthalate) is improved, and the product quality of the paper-plastic composite laminating layer material is ensured.
Detailed Description
Example 1
The embodiment 1 of the invention provides an antibacterial degradable paper-plastic composite coating film layer material which comprises the following raw materials in parts by weight: 70 parts of bio-based plastic, 22 parts of petroleum-based plastic, 5.5 parts of inorganic nano powder, 0.5 part of functional compound and 2 parts of processing aid.
The bio-based plastic is polylactic acid; the weight average molecular weight of the polylactic acid is 20 ten thousand, and the polylactic acid is polylactic acid Ingeo 4032D; the supplier of the polylactic acid Ingeo 4032D is NatureWorks.
The petroleum-based plastic is poly (butylene adipate-terephthalate), and the grade of the poly (butylene adipate-terephthalate) is Ecoworld, which is purchased from Highenh technologies, inc.
The inorganic nano powder comprises an antibacterial agent and a nucleating agent; the mass ratio of the antibacterial agent to the nucleating agent is 5:0.5.
the antibacterial agent is a metal oxide antibacterial agent, the antibacterial agent is nano zinc oxide, the product number of the nano zinc oxide is HSL-PA-3702, and the nano zinc oxide is purchased from Zhongxing nano material Co.
The nucleating agent is an oxide nucleating agent; the oxide nucleating agent is an oxide nucleating agent RQT-CH, and the oxide nucleating agent RQT-CH is purchased from Henan Ruizi Special chemical engineering Co.
The functional compound is a methacrylate compound, and the melt flow rate (190 ℃,2.16 kg) of the methacrylate compound is 35 +/-10 g/10min; the methacrylate compound is a styrene-methacrylate copolymer, the model of which is SG-20, purchased from Korea Polymer (Shanghai) Co., ltd.
The processing aid is a combination of a phosphite antioxidant and a hindered amine light stabilizer, and the mass ratio of the phosphite antioxidant to the hindered amine light stabilizer is 1:1; the phosphite antioxidant is antioxidant-1010, and the hindered amine light stabilizer is UV-770.
The antioxidant 1010 and UV 770 were both purchased from BASF, germany.
In another aspect, embodiment 1 of the present invention provides a preparation method of an antibacterial degradable paper-plastic composite laminated film material, including the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 18min by adopting a high-speed mixer under the condition that the rotating speed is 500rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the material.
The temperature of the twin-screw extruder in the step (2) is 190 ℃, the rotating speed is 250rpm, and the ratio of the length to the diameter of the screw is 40:1.
example 2
The embodiment 2 of the invention provides an antibacterial degradable paper-plastic composite coating layer material which comprises the following raw materials in parts by weight: 80 parts of bio-based plastic, 15 parts of petroleum-based plastic, 3.7 parts of inorganic nano powder, 0.3 part of functional compound and 1 part of processing aid.
The bio-based plastic is polylactic acid; the weight average molecular weight of the polylactic acid is 20 ten thousand, and the polylactic acid is polylactic acid Ingeo 4032D; the supplier of the polylactic acid Ingeo 4032D is NatureWorks.
The petroleum-based plastic is polybutylene adipate-terephthalate, which is sold under the trademark Ecoworld and purchased from Jinhui million Hi-Tech, inc.
The inorganic nano powder comprises an antibacterial agent and a nucleating agent; the mass ratio of the antibacterial agent to the nucleating agent is 3:0.7.
the antibacterial agent is a metal oxide antibacterial agent, the antibacterial agent is nano zinc oxide, the product number of the nano zinc oxide is HSL-PA-3702, and the nano zinc oxide is purchased from Zhongxing nano material Co.
The nucleating agent is an oxide nucleating agent; the oxide nucleating agent is an oxide nucleating agent RQT-CH, and the oxide nucleating agent RQT-CH is purchased from Henan Ruizi Special chemical engineering Co.
The functional compound is a methacrylate compound, and the melt flow rate (190 ℃,2.16 kg) of the methacrylate compound is 35 +/-10 g/10min; the methacrylate compound is styrene-methacrylate copolymer, the model of the styrene-methacrylate copolymer is SG-20, and the styrene-methacrylate copolymer is purchased from the Korea Polymer (Shanghai) Co., ltd.
The processing aid is a combination of a phosphite antioxidant and a hindered amine light stabilizer, and the mass ratio of the phosphite antioxidant to the hindered amine light stabilizer is 1:1; the phosphite antioxidant is antioxidant-1010, and the hindered amine light stabilizer is UV-770.
The antioxidant-1010 and UV-770 were both purchased from BASF corporation, germany.
In another aspect, embodiment 2 of the present invention provides a preparation method of an antibacterial degradable paper-plastic composite laminated film material, including the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 10min by adopting a high-speed mixer under the condition that the rotating speed is 600rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the material.
The temperature of the double-screw extruder in the step (2) is 200 ℃, the rotating speed is 4000rpm, and the ratio of the length to the diameter of the screw is 40:1.
example 3
The embodiment 3 of the invention provides an antibacterial degradable paper-plastic composite coating film layer material which comprises the following raw materials in parts by weight: 88 parts of bio-based plastic, 7 parts of petroleum-based plastic, 3.7 parts of inorganic nano powder, 0.8 part of functional compound and 0.5 part of processing aid.
The bio-based plastic is polylactic acid; the weight average molecular weight of the polylactic acid is 20 ten thousand, and the polylactic acid is polylactic acid Ingeo 4032D; the supplier of the polylactic acid Ingeo 4032D is NatureWorks.
The petroleum-based plastic is polybutylene adipate-terephthalate, which is sold under the trademark Ecoworld and purchased from Jinhui million Hi-Tech, inc.
The inorganic nano powder comprises an antibacterial agent and a nucleating agent; the mass ratio of the antibacterial agent to the nucleating agent is 3:0.7.
the antibacterial agent is a metal oxide antibacterial agent, the antibacterial agent is nano zinc oxide, the product number of the nano zinc oxide is HSL-PA-3702, and the nano zinc oxide is purchased from Zhongxing nano material Co.
The nucleating agent is an oxide nucleating agent; the oxide nucleating agent is an oxide nucleating agent RQT-CH, and the oxide nucleating agent RQT-CH is purchased from Henan Ruizi Special chemical engineering Co.
The functional compound is a methacrylate compound, and the melt flow rate (190 ℃,2.16 kg) of the methacrylate compound is 35 +/-10 g/10min; the methacrylate compound is styrene-methacrylate copolymer, the model of the styrene-methacrylate copolymer is SG-20, and the styrene-methacrylate copolymer is purchased from the Korea Polymer (Shanghai) Co., ltd.
The processing aid is a combination of a phosphite antioxidant and a hindered amine light stabilizer, and the mass ratio of the phosphite antioxidant to the hindered amine light stabilizer is 1:1; the phosphite antioxidant is antioxidant-1010, and the hindered amine light stabilizer is UV-770.
The antioxidant-1010 and UV-770 were both purchased from BASF corporation, germany.
In another aspect, embodiment 3 of the present invention provides a preparation method of an antibacterial degradable paper-plastic composite laminated film material, including the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 10min by adopting a high-speed mixer under the condition that the rotating speed is 800rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the composite material.
In the step (2), the temperature of the double-screw extruder is 220 ℃, the rotating speed is 400rpm, and the ratio of the length to the diameter of the screw is 40:1.
example 4
Embodiment 4 of the invention provides an antibacterial degradable paper-plastic composite coating layer material, which comprises the following raw materials in parts by weight: 94 parts of bio-based plastic, 2 parts of petroleum-based plastic, 2.5 parts of inorganic nano powder, 0.5 part of functional compound and 1 part of processing aid.
The bio-based plastic is polylactic acid; the weight average molecular weight of the polylactic acid is 20 ten thousand, and the polylactic acid is polylactic acid Ingeo 4032D; the supplier of the polylactic acid Ingeo 4032D is NatureWorks.
The petroleum-based plastic is polybutylene adipate-terephthalate, which is sold under the trademark Ecoworld and purchased from Jinhui million Hi-Tech, inc.
The inorganic nano powder comprises an antibacterial agent and a nucleating agent; the mass ratio of the antibacterial agent to the nucleating agent is 5:0.5.
the antibacterial agent is a metal oxide antibacterial agent, the antibacterial agent is nano zinc oxide, the product number of the nano zinc oxide is HSL-PA-3702, and the nano zinc oxide is purchased from Zhongxing nano material Co.
The nucleating agent is an oxide nucleating agent; the oxide nucleating agent is an oxide nucleating agent RQT-CH, and the oxide nucleating agent RQT-CH is purchased from Henan Ruizi Special chemical engineering Co.
The functional compound is a methacrylate compound, and the melt flow rate (190 ℃,2.16 kg) of the methacrylate compound is 35 +/-10 g/10min; the methacrylate compound is styrene-methacrylate copolymer, the model of the styrene-methacrylate copolymer is SG-20, and the styrene-methacrylate copolymer is purchased from the Korea Polymer (Shanghai) Co., ltd.
The processing aid is a combination of a phosphite antioxidant and a hindered amine light stabilizer, and the mass ratio of the phosphite antioxidant to the hindered amine light stabilizer is 1:1; the phosphite antioxidant is antioxidant-1010, and the hindered amine light stabilizer is UV-770.
The antioxidant 1010 and UV 770 were both purchased from BASF, germany.
In another aspect, embodiment 4 of the present invention provides a preparation method of an antibacterial degradable paper-plastic composite laminated film material, including the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 5min by adopting a high-speed mixer under the condition that the rotating speed is 1200rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the composite material.
The temperature of the double-screw extruder in the step (2) is 210 ℃, the rotating speed is 350rpm, and the ratio of the length to the diameter of the screw is 40:1.
performance testing
The antibacterial degradable paper-plastic composite laminated film layer materials prepared in the examples 1-4 are prepared to obtain the antibacterial degradable paper-plastic composite laminated film layer with the thickness of 20 microns, and the tensile property, the biodegradation property and the antibacterial property of the antibacterial degradable paper-plastic composite laminated film layer are tested, and the test results are shown in the following table.
Claims (10)
1. The antibacterial degradable paper-plastic composite laminated film layer material is characterized by at least comprising the following raw materials in parts by weight: 70-98 parts of bio-based plastic, 0.5-30 parts of petroleum-based plastic, 0.6-10 parts of inorganic nano powder, 0.1-1 part of functional compound and 0.1-5 parts of processing aid.
2. The antibacterial degradable paper-plastic composite PE film layer material as claimed in claim 1, wherein the bio-based plastic is at least one selected from polyhydroxyalkanoate, polylactic acid, and polyamino acid.
3. The antibacterial degradable paper-plastic composite PE film layer material as claimed in claim 1, wherein the petroleum-based plastic is selected from one or more of polycaprolactone, polybutylene succinate, polybutylene adipate-terephthalate, and polybutylene succinate-adipate copolymer.
4. The antibacterial degradable paper-plastic composite PE film layer material as claimed in claim 1, wherein the inorganic nanopowder at least comprises an antibacterial agent and a nucleating agent.
5. The antibacterial degradable paper-plastic composite laminated film layer material as claimed in claim 4, wherein the antibacterial agent is one or a mixture of metal ion antibacterial agent, photocatalytic antibacterial agent and metal oxide antibacterial agent.
6. The antibacterial degradable paper-plastic composite laminated film layer material as claimed in claim 4 or 5, wherein the antibacterial agent is a metal ion antibacterial agent or a metal oxide antibacterial agent.
7. The antibacterial degradable paper-plastic composite PE-PE (PE-PE) film layer material as claimed in claim 4, wherein the nucleating agent is one or more of sorbitol nucleating agent, hydrochloric acid nucleating agent, rare earth metal nucleating agent and oxide nucleating agent.
8. The antibacterial degradable paper-plastic composite laminated film layer material as claimed in claim 1, wherein the functional compound is one or more selected from alcohol compounds, amine compounds, methacrylate compounds and epoxy compounds.
9. The antibacterial degradable paper-plastic composite laminated film layer material as claimed in claim 8, wherein the functional compound is a methacrylate compound.
10. The preparation method of the antibacterial degradable paper-plastic composite laminated film material according to any one of claims 1 to 9, characterized by at least comprising the following steps:
(1) Weighing bio-based plastic, petroleum-based plastic, inorganic nano powder, functional compound and processing aid according to parts by weight, and mixing for 5-20 min by adopting a high-speed mixer under the condition that the rotating speed is 300-1500 rpm to obtain a mixture A;
(2) And (2) adding the mixture A obtained in the step (1) into a double-screw extruder, and carrying out plasticizing, dispersing, extruding and granulating to obtain the material.
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