CN105440611A - High-strength and high-toughness polylactic acid composite film with antimicrobial and barrier properties - Google Patents
High-strength and high-toughness polylactic acid composite film with antimicrobial and barrier properties Download PDFInfo
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- CN105440611A CN105440611A CN201510216262.6A CN201510216262A CN105440611A CN 105440611 A CN105440611 A CN 105440611A CN 201510216262 A CN201510216262 A CN 201510216262A CN 105440611 A CN105440611 A CN 105440611A
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Abstract
The present invention relates to high-strength and high-toughness polylactic acid composite film with antimicrobial and barrier properties. Raw materials of the high-toughness polylactic acid composite film comprises polylactic acid, EVOH, polylactic acid grafted glycidyl methacrylate, ethylene-octene copolymer grafted glycidyl methacrylate, eight-arm maleic anhydride POSS, nano TiO2, an antioxidant, and an anti-UV agent. The composite film is formed through multilayer coextrusion. The composite film has excellent strength and toughness, a good oxygen barrier property to gas, and a good antimicrobial effect, and can be used in the field of the environmentally friendly packaging film.
Description
Technical field
The present invention relates to a kind of preparation method of polymeric lactic acid compound film, particularly relate to a kind of high-intensity high-tenacity and there is the preparation method of polymeric lactic acid compound film of high barrier and antibacterial effect thereof.
Background technology
Although plastic material has more excellent performance and suitability widely; but it derives from petroleum products and cannot degrade; in crisis of resource and environmental pollution serious all the more today, find excellent property and reproducible equivalent material then becomes the most important thing of current Material Field research.
In current degradation material, starch is because of its cheap price and originate widely and furtherd investigate and prepared multiple life and industrial goods, as starch basement membrane, starch dishware etc. by modification and compound.But the defect that starch has it natural, its poor mechanical property, unstable properties, can only apply to the field low to mechanical property requirements.And the appearance of poly(lactic acid) changes this present situation.Poly(lactic acid) (PLA) is aliphatic polyester, with lactic acid (2 hydroxy propanoic acid) for basic structural unit.PLA obtains by natural matters such as fermented maizes, and lactic acid polycondensation also can be adopted to obtain.PLA and end product thereof can become CO in natural decomposition under composting conditions
2and water, reducing solid waste discharge amount, is a kind of biogenic material of environmental protection.
Although poly(lactic acid) has good biodegradability, workability, excellent mechanical property, but its property is crisp frangible, lacks flexibility and snappiness, limits the application of poly(lactic acid) to a great extent, and, be in packaging application in the main application of film, its barrier is poor, cannot be applied to the packaging field needing better barrier.Strength modified for polylactic acid membrane, there has been certain research at present, different materials is added in poly(lactic acid) by mode that is blended or chemical modification.As
(WeiZhang, LongChen, the YuZhang such as Zhang Wei; Polymer.2009,50:1311-1315.) blended by polyamide elastomer and poly(lactic acid), poly(lactic acid) snappiness is significantly promoted, but causes the degradation of composite materials property.Chen Zhize etc. have invented a kind of its preparation method (201310393192.2) of transparent high-toughness polylactic acid film, and poly(lactic acid) and methyl MQ silicone resin are total to molten film and form by it, effectively raise the toughness of film.And relate to method that poly(lactic acid) barrier improves and be included in and wherein introduce laminar nano particle such as nano imvite and realize intercalation or other barrier material blended, but its barrier improves still limited, and depend on processing conditions greatly.Meanwhile, as needed polylactic acid membrane to realize multiple packaging character simultaneously, as germ resistance etc., this type of research is still considerably less.
Summary of the invention
The object of the invention is to overcome polylactic acid membrane material fragility large, poor mechanical property and functional single defect, a kind of high-intensity high-tenacity being provided and there is the preparation method of polymeric lactic acid compound film of high barrier and antibacterial effect thereof.
The object of the invention is to be achieved through the following technical solutions:
A kind of tough polymeric lactic acid compound film of height with antibacterial barrier, this composite membrane raw material comprises poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, eight arm maleic anhydride POSS, nano-TiO
2, oxidation inhibitor and anti UV agent, by multi-layer co-extruded film forming.Be further characterized in that:
In raw material, the mass ratio (calculating according to the mass fraction) of each component is:
Poly(lactic acid): 100
EVOH：30-50
Poly(lactic acid) graft glycidyl methacrylate: 5-10
Glycidyl methacrylate graft ethylene octene: 5-10
Eight arm maleic anhydride POSS:2-4
Nano-TiO
2: 2-4.5
Oxidation inhibitor: 2-4
Its preparation technology is:
(1) all raw materials are all descended vacuum-dryings 24 hours in 50 degree, for subsequent use;
(2) by after blended to poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, oxidation inhibitor and anti UV agent high speed, melt extrude, pelletizing obtains masterbatch A, it melt extrudes temperature is 190-210 degree, screw speed is 150-200rad/min, and the residence time is 1-2 minute;
(3) by masterbatch A and POSS compatilizer, nano-TiO
2after high speed is blended, extruded by melt blending, pelletizing obtains masterbatch B, and it melt extrudes temperature is 190-210 degree, and screw speed is 100-150rad/min, and the residence time is 2-3 minute;
(4) masterbatch B is obtained PP TYPE by Multi-layer co-extrusion blow molding machine blown film, blow temperatures is 180-200 DEG C, and blow-up ratio is between 2-4.
Further, the number of plies of described PP TYPE is between 2-5 layer.
Further, described poly(lactic acid) is poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or poly-L, D-ALPHA-Hydroxypropionic acid composition, and the molecular weight of this poly(lactic acid) is between 100,000-30 ten thousand, and optimum, selection molecular weight is between 150,000-25 ten thousand.
Further, the graft(ing) degree of described poly(lactic acid) graft glycidyl methacrylate is between 0.8%-2%.
Further, the molecular weight of glycidyl methacrylate graft ethylene octene involved in the present invention is between 10000-50000, and graft(ing) degree is between 1%-2.2%.
Further, eight arm maleic anhydride POSS involved in the present invention are a kind of silica structures with octahedra cage structure, the radicals R that 8 can be carried out modification is there is in polyhedral oligomeric silsesquioxane (POSS) on the corner of cage structure, in the present invention, R group is maleic, and the molecular structural formula of eight arm maleic anhydride POSS is as follows:
Further, described nano-TiO
2size between 10-200nm, crystal formation is anatase titanium dioxide.
Further, described oxidation inhibitor is antioxidant 264, BHT, 168, and one or more in 1010.
Further, beneficial effect of the present invention is, first, there is flexible EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate adds the flexibility that improve composite membrane, and poly(lactic acid) graft glycidyl methacrylate can have good fusion in poly(lactic acid), and POE graft glycidyl methacrylate connects poly(lactic acid) graft glycidyl methacrylate on the one hand, connect EVOH on the other hand, composite membrane matrix resin is made to have good consistency, be conducive to the realization of overall performance.Secondly, nano-TiO
2introducing both achieved and effectively improving barrier properties for gases, its anatase titanium dioxide crystal formation is also conducive to the realization of its germ resistance.Eight arm maleic anhydride POSS play the effect of compatilizer, effectively can improve nano-TiO
2dispersion in composite membrane, itself adds the also favourable raising with composite membrane mechanical property.Finally, multi-layer co-extrudedly compound film strength and oxygen-barrier property can effectively be improved further.
Embodiment
Below will describe illustrative embodiment of the present invention in detail.But these implementation methods are only exemplary object, and the present invention is not limited thereto.
Embodiment 1
A kind of tough polymeric lactic acid compound film of height with antibacterial barrier, this film raw material comprises poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, eight arm maleic anhydride POSS, nano-TiO
2, oxidation inhibitor and anti UV agent.By multi-layer co-extruded film forming.Be further characterized in that:
In raw material, the mass ratio (calculating according to the mass fraction) of each component is:
Poly(lactic acid): 100
EVOH：45
Poly(lactic acid) graft glycidyl methacrylate: 8.4
Glycidyl methacrylate graft ethylene octene: 7.6
Eight arm maleic anhydride POSS:2.8
Nano-TiO
2: 3.6
Oxidation inhibitor: 2.5
Its preparation technology is:
(1) all raw materials are all descended vacuum-dryings 24 hours in 50 degree, for subsequent use;
(2) by after blended to poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, oxidation inhibitor and anti UV agent high speed, melt extrude.Pelletizing obtains masterbatch A, and it melt extrudes temperature is 190-210 degree, and screw speed is 180rad/min, and the residence time is 1.5 minutes;
(3) by masterbatch A and POSS compatilizer, nano-TiO
2after high speed is blended, extruded by melt blending.Pelletizing obtains masterbatch B, and it melt extrudes temperature is 190-210 degree, and screw speed is 120rad/min, and the residence time is 2.5 minutes;
(4) masterbatch B is obtained PP TYPE by Multi-layer co-extrusion blow molding machine blown film, blow temperatures is 190 degree, and it is 3.5 that blow-up ratio controls.
The number of plies of described PP TYPE is 3 layers.
Described poly(lactic acid) is poly (l-lactic acid), and the molecular weight of this poly(lactic acid) is between 120,000-20 ten thousand.
The graft(ing) degree of described poly(lactic acid) graft glycidyl methacrylate is 1.4%, and molecular weight is 14.5 ten thousand.
The molecular weight of described glycidyl methacrylate graft ethylene octene is 25000, and graft(ing) degree is 1.8%.
Described nano-TiO
2size between 20-100nm, crystal formation is anatase titanium dioxide.
Described oxidation inhibitor is antioxidant 264.
Specific performance is as shown in table 1.
Embodiment 2
A kind of tough polymeric lactic acid compound film of height with antibacterial barrier, this film raw material comprises poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, eight arm maleic anhydride POSS, nano-TiO
2, oxidation inhibitor and anti UV agent.By multi-layer co-extruded film forming.Be further characterized in that:
In raw material, the mass ratio (calculating according to the mass fraction) of each component is:
Poly(lactic acid): 100
EVOH：35
Poly(lactic acid) graft glycidyl methacrylate: 7.5
Glycidyl methacrylate graft ethylene octene: 7.5
Eight arm maleic anhydride POSS:3.2
Nano-TiO
2: 4
Oxidation inhibitor: 3
Its preparation technology is:
(1) all raw materials are all descended vacuum-dryings 24 hours in 50 degree, for subsequent use;
(2) by after blended to poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, oxidation inhibitor and anti UV agent high speed, melt extrude.Pelletizing obtains masterbatch A, and it melt extrudes temperature is 190-210 degree, and screw speed is 180rad/min, and the residence time is 1.5 minutes;
(3) by masterbatch A and POSS compatilizer, nano-TiO
2after high speed is blended, extruded by melt blending.Pelletizing obtains masterbatch B, and it melt extrudes temperature is 190-210 degree, and screw speed is 120rad/min, and the residence time is 2.5 minutes;
(4) masterbatch B is obtained PP TYPE by Multi-layer co-extrusion blow molding machine blown film, blow temperatures is 180-200 DEG C, and it is 3.2 that blow-up ratio controls.
The number of plies of described PP TYPE is 4 layers.
Described poly(lactic acid) is poly-D-ALPHA-Hydroxypropionic acid, and the molecular weight of this poly(lactic acid) is between 150,000-25 ten thousand.
The graft(ing) degree of described poly(lactic acid) graft glycidyl methacrylate is 1.6%, and molecular weight is 16.4 ten thousand.
The molecular weight of described glycidyl methacrylate graft ethylene octene is 32000, and graft(ing) degree is 1.6%.
Described nano-TiO
2size between 20-150nm, crystal formation is anatase titanium dioxide.
Described oxidation inhibitor is antioxidant BHT.
Specific performance is as shown in table 1.
The performance of composite membrane prepared by table 1, embodiment 1,2
| Composite property | Embodiment 1 | Embodiment 2 |
| Tension set (%) | 104±10 | 103±10 |
| Breaking tenacity (Mpa) | 63.4±4.34 | 68.6±3.51 |
| Oxygen transit dose (cm 3/m 2·24h·0.1MPa） | 16±4 | 18±5 |
Claims (5)
1. one kind has the tough polymeric lactic acid compound film of height of antibacterial barrier, this composite membrane raw material comprises poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, eight arm maleic anhydride POSS, nano-TiO
2, oxidation inhibitor and anti UV agent, by multi-layer co-extruded film forming, be further characterized in that:
In raw material, the mass ratio (calculating according to the mass fraction) of each component is:
Poly(lactic acid): 100
EVOH：30-50
Poly(lactic acid) graft glycidyl methacrylate: 5-10
Glycidyl methacrylate graft ethylene octene: 5-10
Eight arm maleic anhydride POSS:2-4
Nano-TiO
2: 2-4.5
Oxidation inhibitor: 2-4
Its preparation technology is:
(1), by all raw materials all in 50 degree of lower vacuum-dryings 24 hours, for subsequent use;
(2), by after blended to poly(lactic acid), EVOH, poly(lactic acid) graft glycidyl methacrylate, POE graft glycidyl methacrylate, oxidation inhibitor and anti UV agent high speed, melt extrude, pelletizing obtains masterbatch A, it melt extrudes temperature is 190-210 degree, screw speed is 150-200rad/min, and the residence time is 1-2 minute;
(3), by masterbatch A and POSS compatilizer, nano-TiO
2after high speed is blended, extruded by melt blending, pelletizing obtains masterbatch B, and it melt extrudes temperature is 190-210 degree, and screw speed is 100-150rad/min, and the residence time is 2-3 minute;
(4), by masterbatch B obtain PP TYPE by Multi-layer co-extrusion blow molding machine blown film, blow temperatures is 180-200 DEG C, and blow-up ratio is between 2-4.
2. a kind of tough polymeric lactic acid compound film of height with antibacterial barrier as claimed in claim 1, it is characterized in that, the number of plies of described PP TYPE is between 2-5 layer.
3. a kind of tough polymeric lactic acid compound film of height with antibacterial barrier as claimed in claim 1, it is characterized in that, the molecular weight of described glycidyl methacrylate graft ethylene octene is between 10000-50000, and graft(ing) degree is between 1%-2.2%.
4. a kind of tough polymeric lactic acid compound film of height with antibacterial barrier as claimed in claim 1, it is characterized in that, the graft(ing) degree of described poly(lactic acid) graft glycidyl methacrylate is between 0.8%-2%.
5. a kind of tough polymeric lactic acid compound film of height with antibacterial barrier as claimed in claim 1, is characterized in that, nano-TiO
2size between 10-200nm, crystal formation is anatase titanium dioxide.
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| CN105907063A (en) * | 2016-05-20 | 2016-08-31 | 苏州倍力特物流设备有限公司 | Antibacterial biological nano packaging film and preparation method thereof |
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| CN106867222A (en) * | 2017-02-21 | 2017-06-20 | 湖南工业大学 | A kind of anti-tear food package film of degradable tension |
| CN110358273A (en) * | 2019-08-13 | 2019-10-22 | 湖南工业大学 | A kind of biomass antibacterial film with high puncturing resistance performance |
| CN115975355A (en) * | 2022-12-29 | 2023-04-18 | 广州市信联包装容器实业有限公司 | High-barrier-toughness PET (polyethylene terephthalate) -based composite film and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105907063A (en) * | 2016-05-20 | 2016-08-31 | 苏州倍力特物流设备有限公司 | Antibacterial biological nano packaging film and preparation method thereof |
| CN106854283A (en) * | 2016-12-22 | 2017-06-16 | 常州百佳薄膜科技有限公司 | A kind of nanometer barrier additive and preparation method thereof and Related product |
| CN106854283B (en) * | 2016-12-22 | 2019-08-06 | 常州百佳年代薄膜科技股份有限公司 | A kind of nanometer barrier additive and preparation method thereof and Related product |
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| CN106867222A (en) * | 2017-02-21 | 2017-06-20 | 湖南工业大学 | A kind of anti-tear food package film of degradable tension |
| CN106867222B (en) * | 2017-02-21 | 2018-08-07 | 湖南工业大学 | A kind of anti-tear food package film of degradable tension |
| CN110358273A (en) * | 2019-08-13 | 2019-10-22 | 湖南工业大学 | A kind of biomass antibacterial film with high puncturing resistance performance |
| CN115975355A (en) * | 2022-12-29 | 2023-04-18 | 广州市信联包装容器实业有限公司 | High-barrier-toughness PET (polyethylene terephthalate) -based composite film and preparation method and application thereof |
| CN115975355B (en) * | 2022-12-29 | 2024-05-07 | 广州市信联包装容器实业有限公司 | PET-based composite film with high barrier strength and toughness, and preparation method and application thereof |
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Effective date of registration: 20210319 Address after: No.3, Tianhua South Road, Changsha Economic and Technological Development Zone, Changsha, Hunan 410000 Patentee after: HUNAN YIYONGFENG PRINGTING PACKAGING Co.,Ltd. Address before: 412008 No. 88 Taishan Road, Tianyuan District, Zhuzhou City, Hunan Province Patentee before: HUNAN University OF TECHNOLOGY |
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Address after: No.3, Tianhua South Road, Changsha Economic and Technological Development Zone, Changsha, Hunan 410000 Patentee after: Hunan yiyongfeng New Material Technology Co.,Ltd. Address before: No.3, Tianhua South Road, Changsha Economic and Technological Development Zone, Changsha, Hunan 410000 Patentee before: HUNAN YIYONGFENG PRINGTING PACKAGING Co.,Ltd. |