CN102268178A - Transparent plasticized polylactic acid nano resin slice with low mobility and preparation method thereof - Google Patents
Transparent plasticized polylactic acid nano resin slice with low mobility and preparation method thereof Download PDFInfo
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- CN102268178A CN102268178A CN 201110141825 CN201110141825A CN102268178A CN 102268178 A CN102268178 A CN 102268178A CN 201110141825 CN201110141825 CN 201110141825 CN 201110141825 A CN201110141825 A CN 201110141825A CN 102268178 A CN102268178 A CN 102268178A
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Abstract
The invention relates to a transparent plasticized polylactic acid nano resin slice with low mobility and a preparation method thereof. The transparent plasticized polylactic acid nano resin slice with low mobility comprises, by weight, 30-97.5 parts of polylactic acid, 1-30 parts of plasticizer, 1-30 parts of nano particle, 0-10 parts of nano particle modifier and 0.5-10 parts of chain extender. The preparation method comprises steps of: mixing polylactic acid, a chain extender and a plasticizer; then adding nano inorganic particles and a nano inorganic particle modifier; and mixing well and carrying out melt blending granulation to obtain the transparent plasticized polylactic acid nano resin slice with low mobility. The plasticized polylactic acid nano resin slice of the invention is a completely biodegraded material with excellent mechanical properties, can obviously improve defects of weak toughness and brittleness of polylactic acid, and can be used in preparation of a plurality of plastic products, such as stationery, toy, tableware and agricultural mulch film, etc. The preparation method of the present invention is simple, at low costs and suitable for large-scale production.
Description
Technical field
The invention belongs to blending and modifying poly(lactic acid) and preparation field thereof, particularly a kind of transparent low mobility plasticized poly lactic acid nano-resin section and preparation method thereof.
Background technology
Plastics have light weight, waterproof, durable, production technology is ripe, low cost and other advantages, since coming out, bring many facilities to people, but simultaneously also produce serious day by day pollution problem, landfill in the past, burning, recycling be contaminated solution problem fundamentally all.In petrochemical industry resources such as oil, coal exhausted day by day today, The biological resources development and use the extensive concern that has been subjected to people.According to U.S. ASTM definition, biodegradable material is the material that degraded takes place by nature microorganism (bacterium, fungi etc.) effect.In general, biodegradable material is meant in biological and biochemical action process or the material that can degrade in the coenocorrelation.In the biodegradable material polymer, starch, poly(lactic acid) (PLA), poly-(PHB) etc. are raw material with biological renewable resources, can reduce the dependence of polymer preparation to oil, therefore are subjected to paying close attention to more widely.
With reproducible Biological resources is the poly(lactic acid) of raw material, can break away from dependence to petroleum resources, and poly(lactic acid) still is a kind of less energy-consumption product, the low 30%-50% of petroleum base polymer such as its manufacturing process energy loss-rate polyethylene, polystyrene, polylactic acid article after the use through burning, composting, processing such as bury, can reduce Carbon emission too much in atmosphere to carbonic acid gas return to the nature circle, thereby reduce the content of Carbon Dioxide in Air.Therefore, PLA is the material of a kind of low-carbon (LC), environmental protection, Sustainable development.
PLA has very high intensity and modulus, rigidity maximum in biodegradable polymer, but drawbacks limit such as its fragility is big, poor heat stability, melt strength are low its range of application, therefore need carry out modification to it.Chinese patent 200510050275.7 discloses a kind of method for preparing resin granules of poly lactic acid by the adding softening agent.Chinese patent 201010296257.8 discloses the material modified preparation method of a kind of poly(lactic acid) and softening agent and nano inoganic particle blend.Can effectively improve the snappiness of PLA by traditional blend plasticization and modification PLA, yet the intensity of material and modulus can reduce significantly, and there is the plasticizer migration phenomenon in Plasticising system, thereby has influenced the storage and the use of plasticising PLA material after after a while.The present invention utilizes chainextender to make softening agent and poly(lactic acid) form segmented copolymer, effective plasticized poly lactic acid not only, and reduced migration of plasticizer, simultaneously by with the nano particle blend of nano particle and/or modification, can improve thermotolerance, wear resistance, dimensional stability, rigidity and the workability of goods, and reduce cost.
Summary of the invention
Technical problem to be solved by this invention provides a kind of transparent low mobility plasticized poly lactic acid nano-resin section and preparation method thereof, this polylactic acid nano resin slicer is a full-biodegradable material, and has excellent mechanical property, and this preparation method is simple, cost is low, can be mass-produced.
A kind of transparent low mobility plasticized poly lactic acid nano-resin section of the present invention, its component comprises by weight:
Preferably comprising by weight of the component of above-mentioned polylactic acid nano resin slicer: poly(lactic acid) 50-78 part, softening agent 15-25 part, nanoparticle 5-15 part, nanometer particle-modified dose of 1-5 part, chainextender 1-5 part.
Above-mentioned softening agent is one or more in dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), tributyl acetylcitrate (ATBC), trioctyl lemon acid (TOC), acetyl tributyl citrate three monooctyl esters (ATOC), triphenylphosphate (TPPi), Uniflex DBS (DBS), the polyoxyethylene glycol (molecular weight 600-20000).
Above-mentioned nanoparticle is one or more in talcum powder, silicon-dioxide, lime carbonate, polynite, kaolin, the diatomite.
Above-mentioned nanometer particle-modified dose is in maleic anhydride, gamma-amino propyl-triethylsilicane oxygen alkane (KH-550), γ-glycidyl ether propyl trimethoxy silicane (KH-560), γ-(methyl acetoxyl group) propyl trimethoxy silicane (KH570), vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171), stearate, titanic acid ester, the aluminic acid ester one or more.
Above-mentioned chainextender is diglycidyl ether class ring-type diepoxide, 4-tetrahydrobenzene-1,2-dicarboxylic acid (epoxy ethyl methyl) ester, hexamethylene diisocyanate (1,6-HDI), diphenylmethanediisocyanate (MDI), isoflurane chalcone diisocyanate (IPDI), 1,3-phenyl-two (2-oxazoline), 1, one or more in 4-phenyl-two (2-oxazoline), two (the 2-oxazolines).
The preparation method of a kind of transparent low mobility plasticized poly lactic acid nano-resin section of the present invention comprises:
By weight poly(lactic acid) 30-97.5 part, chainextender 0.5-10 part and softening agent 1-30 part are mixed, add nano inoganic particle 1-30 part and nano inoganic particle modified dose of 0-10 part then, carry out the melt blending granulation after mixing, promptly get this transparent low mobility plasticized poly lactic acid nano-resin section.
Above-mentioned being blended in kneader or the high-speed mixer finished, and its rotating speed is 200～3000rpm, mixing time 10～3000 seconds.
What above-mentioned melt blending granulation was adopted is twin screw blend forcing machine, and wherein respectively to distinguish temperature be 140～190 ℃ to twin screw blend forcing machine, and screw speed is 60～300rpm.
After the present invention at first carries out mechanically mixing with poly(lactic acid), softening agent, nano inoganic particle, modified by nano particles agent, chainextender, obtain transparent low mobility plasticized poly lactic acid nano-resin section with the twin screw extruder melt pelletization again.Polylactic resin of the present invention is a full-biodegradable material, and has excellent mechanical property, can obviously improve the toughness of poly(lactic acid) and the defective of fragility difference.
The present invention utilizes chainextender to make softening agent and poly(lactic acid) form segmented copolymer, effective plasticized poly lactic acid not only, and reduced migration of plasticizer, simultaneously by with the nano particle blend of nano particle and/or modification, can improve thermotolerance, wear resistance, dimensional stability, rigidity and the workability of goods, and reduce cost.The preparation method is simply effective, can scale operation, can be used in the preparation of multiple plastics, for example fields such as stationery, toy, tableware, agricultural mulching.
Beneficial effect:
(1) transparent low mobility plasticized poly lactic acid nano-resin section of the present invention is full-biodegradable material, and has an excellent mechanical property, can obviously improve the toughness of poly(lactic acid) and the defective of fragility difference, can be used in the preparation of multiple plastics, for example fields such as stationery, toy, tableware, agricultural mulching.
(2) preparation method of the present invention is simple, and cost is low, can be mass-produced.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With PLA particle, talcum powder through vacuum-drying, to moisture content be 100ppm-150ppm, with 790g poly(lactic acid), 150g polyoxyethylene glycol (molecular weight 1000-2000), 10g hexamethylene diisocyanate (1,6-HDI) in high-speed mixer, mixed 20 seconds, the rotating speed of high-speed mixer is 500rpm, adds 50g modified Nano particle talcum powder then and mixes 50 seconds.Carry out melt blending with twin screw extruder then, extrusion temperature is 170 ℃, and screw speed is 100rpm, granulation after cooling drying get final product.
Embodiment 2
With PLA particle, lime carbonate through vacuum-drying, to moisture content be 100ppm-150ppm, 685g poly(lactic acid), 200g polyoxyethylene glycol (molecular weight 5000-10000), 15g isoflurane chalcone diisocyanate (IPDI) were mixed 15 seconds in high-speed mixer, the rotating speed of high-speed mixer is 1000rpm, adds 50g nanoparticle lime carbonate and 50g nano inoganic particle talcum powder then and mixes 100 seconds.Carry out melt blending with twin screw extruder then, extrusion temperature is 160 ℃, and screw speed is 80rpm, granulation after cooling drying get final product.
Embodiment 3
With PLA particle, silicon-dioxide through vacuum-drying, to moisture content be 200ppm-250ppm, 550g poly(lactic acid), 50g polyoxyethylene glycol (molecular weight 600-1500), 300g isoflurane chalcone diisocyanate (IPDI) were mixed 100 seconds in high-speed mixer, the rotating speed of high-speed mixer is 1500rpm, adds nanometer particle-modified dose of maleic anhydride of 80g nanoparticle silicon-dioxide and 20g then and mixes 100 seconds.With twin screw blend forcing machine extruding pelletization, extrusion temperature is 180 ℃, and screw speed is 120rpm.Cooling drying gets final product then.
Embodiment 4
With PLA particle, talcum powder through vacuum-drying, to moisture content be 300ppm-350ppm, with 635g poly(lactic acid), 200g tributyl acetylcitrate (ATBC), 15g 1,3-phenyl-two (2-oxazoline) mixed 20 seconds in high-speed mixer, the rotating speed of high-speed mixer is 2000rpm, adds 150g nano inoganic particle talcum powder then and mixes 150 seconds.With twin screw blend forcing machine extruding pelletization, extrusion temperature is 190 ℃, and screw speed is 130rpm.Cooling drying gets final product then.
Embodiment 5
With PLA particle, polynite through vacuum-drying, to moisture content be 400ppm-500ppm, with 580g poly(lactic acid), 250g trioctyl lemon acid (TOC), 20g1,3-phenyl-two (2-oxazoline) mixed 2000 seconds in high-speed mixer, the rotating speed of high-speed mixer is 2500rpm, adds the polynite of 150g nanoparticle then and mixes 150 seconds.With twin screw blend forcing machine extruding pelletization, extrusion temperature is 150 ℃, and screw speed is 250rpm.Cooling drying gets final product then.
Claims (9)
1. transparent low mobility plasticized poly lactic acid nano-resin section, its component comprises: poly(lactic acid), softening agent, nanoparticle, nanometer particle-modified dose and chainextender.
2. a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 1, it is characterized in that: the component of this polylactic acid nano resin slicer comprises by weight: poly(lactic acid) 30-97.5 part, softening agent 1-30 part, nanoparticle 1-30 part, nanometer particle-modified dose of 0-10 part, chainextender 0.5-10 part.
3. a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 1, it is characterized in that: described softening agent is one or more in dioctyl phthalate (DOP), dibutyl phthalate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, trioctyl lemon acid, acetyl tributyl citrate three monooctyl esters, triphenylphosphate, Uniflex DBS, the polyoxyethylene glycol.
4. a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 1, it is characterized in that: described nanoparticle is one or more in talcum powder, silicon-dioxide, lime carbonate, polynite, kaolin, the diatomite.
5. a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 1 is characterized in that: described nanometer particle-modified dose is in maleic anhydride, gamma-amino propyl-triethylsilicane oxygen alkane, γ-glycidyl ether propyl trimethoxy silicane, γ-(methyl acetoxyl group) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane, stearate, titanic acid ester, the aluminic acid ester one or more.
6. a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 1, it is characterized in that: described chainextender is diglycidyl ether class ring-type diepoxide, 4-tetrahydrobenzene-1,2-dicarboxylic acid (epoxy ethyl methyl) ester, hexamethylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, 1,3-phenyl-two (2-oxazoline), 1, one or more in 4-phenyl-two (2-oxazoline), two (the 2-oxazolines).
7. the preparation method of a transparent low mobility plasticized poly lactic acid nano-resin section comprises:
By weight poly(lactic acid) 30-97.5 part, chainextender 0.5-10 part and softening agent 1-30 part are mixed, add nano inoganic particle 1-30 part and nano inoganic particle modified dose of 0-10 part then, carry out the melt blending granulation after mixing, promptly get this transparent low mobility plasticized poly lactic acid nano-resin section.
8. the preparation method of a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 6, it is characterized in that: described being blended in kneader or the high-speed mixer finished, its rotating speed is 200～3000rpm, mixing time 10～3000 seconds.
9. the preparation method of a kind of transparent low mobility plasticized poly lactic acid nano-resin section according to claim 6, it is characterized in that: what described melt blending granulation was adopted is twin screw blend forcing machine, wherein respectively to distinguish temperature be 140～190 ℃ to twin screw blend forcing machine, and screw speed is 60～300rpm.
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Cited By (7)
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| CN103665802A (en) * | 2013-11-29 | 2014-03-26 | 成都新柯力化工科技有限公司 | Preparation method of polylactic acid material for 3D (three-dimensional) printing |
| CN104262915A (en) * | 2014-09-16 | 2015-01-07 | 中国林业科学研究院林产化学工业研究所 | Method for preparing low-mobility polylactic-acid-base plasticizing wood-plastic composite material |
| CN107778463A (en) * | 2017-12-05 | 2018-03-09 | 桐乡守敬应用技术研究院有限公司 | A kind of nano montmorillonite modified PLA |
| WO2019100713A1 (en) * | 2017-11-27 | 2019-05-31 | 金发科技股份有限公司 | Polylactic acid composite material and application thereof |
| CN111234482A (en) * | 2018-11-29 | 2020-06-05 | 东华大学 | Preparation method of polylactic acid/nano jade powder mixture and high-speed mixing device thereof |
| CN113462135A (en) * | 2021-07-16 | 2021-10-01 | 濮阳市华乐科技有限公司 | Composite polylactic acid modified material |
| CN115387023A (en) * | 2022-08-02 | 2022-11-25 | 广东汇齐新材料有限公司 | Preparation method of TPU/PLA melt-blown composite non-woven fabric |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665802A (en) * | 2013-11-29 | 2014-03-26 | 成都新柯力化工科技有限公司 | Preparation method of polylactic acid material for 3D (three-dimensional) printing |
| CN103665802B (en) * | 2013-11-29 | 2015-09-02 | 成都新柯力化工科技有限公司 | A kind of preparation method of the poly-lactic acid material for 3D printing |
| CN104262915A (en) * | 2014-09-16 | 2015-01-07 | 中国林业科学研究院林产化学工业研究所 | Method for preparing low-mobility polylactic-acid-base plasticizing wood-plastic composite material |
| WO2019100713A1 (en) * | 2017-11-27 | 2019-05-31 | 金发科技股份有限公司 | Polylactic acid composite material and application thereof |
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| CN107778463A (en) * | 2017-12-05 | 2018-03-09 | 桐乡守敬应用技术研究院有限公司 | A kind of nano montmorillonite modified PLA |
| CN111234482A (en) * | 2018-11-29 | 2020-06-05 | 东华大学 | Preparation method of polylactic acid/nano jade powder mixture and high-speed mixing device thereof |
| CN113462135A (en) * | 2021-07-16 | 2021-10-01 | 濮阳市华乐科技有限公司 | Composite polylactic acid modified material |
| CN115387023A (en) * | 2022-08-02 | 2022-11-25 | 广东汇齐新材料有限公司 | Preparation method of TPU/PLA melt-blown composite non-woven fabric |
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Application publication date: 20111207 |