CN101037532A - Toughened and reinforced polylactic acid nano composite material and preparation method thereof - Google Patents
Toughened and reinforced polylactic acid nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to method of preparing secondary functionalization organic modified montmorillonite (TFC), toughening and reinforcement biodegradable polylactic acid nano composite material using the organic montmorillonite and preparing method thereof. The novel double-function group organic modified montmorillonite (TFC) enhances adhesion force between montmorillonite and polymer molecule and obviously increases property of the composite material. The toughening and reinforcement biodegradable polylactic acid nano composite material is prepared by using polylactic acid as main raw material, and adding certain poly(epsilon-caprolactone) and lactic acid-epsilon-caprolactone copolymer; plasticizer selects acetyl tri-n-butyl citrate, tri-n-butyl citrate, triethyl citrate, dioctyl phthalate, and dibutylphthalate; lubricant selects aluminum stearate and calcium stearate; heat stabilizer selects maleic anhydride and epoxy soybean oil (EOS); and intensifier selects TFC montmorillonite (MMT). The prepared composite material possesses high strength and good toughness, and is hopeful of replacing traditional non-degradable material to be applied in field such as packaging, medical, and engineering for solving environment problems generated by white pollution.
Description
Technical field
The present invention relates to a kind of biodegradable polylactic acid blend nano composite material and preparation method thereof, belong to poyblend/laminated nm-silicate composite material preparing technical field.
Background technology
Poly(lactic acid) (PLA) belongs to synthetic straight chain aliphatic polyester, is a kind of artificial-synthetic copolymer at the nature fully biodegradable.Its synthon lactic acid extensively derives from agricultural-food, and degraded product is the water and the carbonic acid gas of environmental sound.This material has good mechanical intensity, thermoplasticity, fiberizability and the transparency, is applicable to multiple working method, is thought the most promising type material of new millennium by industrial community.But pure poly(lactic acid) this as linear polymer, fragility height, heat-drawn wire low (under the 0.46MPa load is 54 ℃), shock resistance is poor, barrier properties for gases and flame retardant resistance are not high, and degradation cycle is difficult to control, and these shortcomings have all limited the further application of poly(lactic acid).
The traditional polymer method of modifying comprises and adds mineral filler with other polymer blending or in polymeric matrix, but these methods can only be improved the performance of some aspect of matrix polymer, often attend to one thing and lose sight of another, and over-all properties is relatively poor.Use clay of laminar silicate, especially polynite, carry out intercalation, polymer molecule is entered between clay seam, form the microcosmic nanostructure, it is big to show nano material intensity, the peculiar property of good toughness.If polymer blending technology and polyalcohol intercalation technology are combined, then the advantage of two kinds of technology can be carried out complementation, learn from other's strong points to offset one's weaknesses, make matrix material reach desired good over-all properties.
The natural montmorillonite interlayer is a hydrophilic environment, and hydrophobic polymer molecule is difficult to enter, therefore need be to polynite to processing that organise, and this is the key of polymer materials formation nanostructure.Existing method of modifying is general to use a kind of organic cation to realize by ion-exchange, but the cationic adhesive effect of long-chain fat family between polymkeric substance and cheating engaging layer is often not remarkable.
Patent CN03149911.2 has introduced a kind of preparation method of biodegradable resin matrix material, (5～50wt%) wait and prepare matrix material to use poly(lactic acid) and polynite, mica and talcum, its modulus in flexure and flame retardant properties have raising in various degree, but, do not describe in detail such as intensity, toughness etc. for other key property.Patent CN200510030494.9 has introduced a kind of method of novel dispersion polynite, and the intensity of the material of some proportioning and thermotolerance have an amount of raising.But PLA and PCL are as the inconsistent Biodegradable high-molecular blend of a pair of thermodynamics, and phase-splitting often appears in material microstructure, cause some degradation obvious, and the over-all properties of material also has the space of further improving.
In sum, comprehensively using new technique means and type material is to solve above-mentioned materials performance process and performance deficiency, prepares the key of the more superior Biodegradable nanometer matrix material of over-all properties.
Summary of the invention
One of purpose of the present invention is to provide a kind of enhancing plasticizing polylactic acid nano composite material.
Two of purpose of the present invention is to provide the preparation method of this matrix material.
For achieving the above object, the means that the present invention uses polymer blending and polyalcohol intercalation to combine, and the segmented copolymer that adds secondary function modified organo montmorillonite TFC (Twice Functionalized Clay) and promote the polymkeric substance relative consistency, prepare and have good mechanical strength and flexible nano composite material.
According to above-mentioned principle, the present invention adopts following technical scheme:
A kind of toughness reinforcing enhancing poly lactic acid nano composite material is characterized in that having used the modified organo montmorillonite TFC of secondary functionization, and the composition of this matrix material and quality percentage composition are:
Poly(lactic acid) 60～90% toughner 5～20%
1～20 part of thermo-stabilizer 0～0.1% of expanding material
1～10 part of lubricant 0～0.1% of modified organo montmorillonite;
Wherein, described modified organo montmorillonite prepares as follows:
I. Na polynite and alkylamine are pressed 100: the mass ratio of 1-5, be dispersed in 70～90 ℃ of deionized waters, and the mass percent concentration that makes the Na polynite continued vigorous stirring 3～5 hours less than 8%; After filtration, the washing back is standby;
Ii. under 70～90 ℃, following component is mixed by following mass percent, refluxed again 3～5 hours; Through suction filtration, behind the deionized water wash,, after grinding, the sieve through 100～300 gets modified organo montmorillonite TFC 100～105 ℃ of oven dry down; Component utilized and mass percent are:
Through step a gained modified montmorillonoid 5～20%,
80%～95% aqueous ethanolic solution 70～95%,
Silane coupling agent 1～5%,
0.1mol/L concentrated hydrochloric acid 0.01～0.05%.
The viscosity-average molecular weight of above-mentioned poly(lactic acid) is 150～4,000,000, and glass temperature range is 40～60 ℃, and the melt temperature scope is 150～210 ℃; Described toughner is: biodegradable polymers class or softening agent class; Described expanding material comprises: PLA-PCL-PLA, PLA-PEO-PLA, PLA-PHB-PLA, PLA-PGA-PLA, any one or two kinds of above segmented copolymers among the PLA-PEO-PLA; Described alkylamine is organically-modified cationite; Described silane coupling agent is a gamma-amino propyl-triethylsilicane oxygen alkane (KH-550), γ-glycidyl ether propyl trimethoxy silicane (KH-560), 3-(2-aminoethyl)-aminopropyl methyl dimethoxysilane (SCA-602), one or several in the vinyltriethoxysilane (A-151); Described thermo-stabilizer is MALEIC ANHYDRIDE or epoxy soybean oil; Described lubricant is aluminum stearate or calcium stearate.
Above-mentioned biodegradable polymers class toughner is: poly-(6-caprolactone), polyoxyethylene, poly-hydroxy fatty acid butyl ester, polyglycolic acid, molecular weight are any one or two kinds of above mixtures in 300～4000 the polyoxyethylene glycol; Described softening agent class toughner is: any one or two kinds of above mixtures in ATBC, tri-n-butyl citrate, triethyl citrate, dioctyl phthalate (DOP), the dibutyl phthalate; Described organically-modified cationite is: heptadecyl carboxyl ammonium chloride, octadecyl ammonium chloride, octadecyl double hydroxyethyl ammonio methacrylate, a kind of or mixture more than two kinds in the distearyl dimethyl ammonium chloride.
The preparation method of above-mentioned toughness reinforcing enhancing poly lactic acid nano composite material is characterized in that the concrete steps of this method are:
A. Na polynite and alkylamine are pressed 100: the mass ratio of 1-5, be dispersed in 70～90 ℃ of deionized waters, and the mass percent concentration that makes the Na polynite continued vigorous stirring 3～5 hours less than 8%; After filtration, the washing back is standby;
B. under 70～90 ℃, following component is mixed by following mass percent, refluxed again 3～5 hours; Through suction filtration, behind the deionized water wash,, after grinding, 100～300 purpose sieve get modified organo montmorillonite 100～105 ℃ of oven dry down; Component utilized and mass percent are:
Through step a gained modified montmorillonoid 5～20%,
80%～95% aqueous ethanolic solution 70～95%,
Silane coupling agent 1～5%,
0.1mol/L concentrated hydrochloric acid 0.01～0.05%;
C. strengthen the preparation of plasticizing polylactic acid nano composite material: according to the component and the proportioning of above-mentioned matrix material, use torque rheometer at 140～210 ℃, rotating speed is to carry out the melt blending intercalation under 20～50rpm condition 3～6 minutes, and then be to carry out melt blending intercalation 3～6min under 50～100rpm condition at rotating speed, coldmoulding 8～20 minutes, be incubated 1～5 hour down at 100～110 ℃ at last, the plasticizing polylactic acid nano composite material promptly is enhanced.
Compared with prior art, the present invention has following conspicuous outstanding feature and marked improvement:
(1) because matrix material of the present invention comprises that poly(lactic acid) is a main raw material, other biodegradable polymers or softening agent are toughner, with derive from natural polynite and carry out intercalation and strengthen, as seen this matrix material be a green fully, the material of totally biodegradable.
(2) the imvite modified method of tradition is improved, introduced another target functional group, increased between cheating engaging layer and the bonding force between the polymkeric substance, make intercalation effect improve obviously by the secondary function modification.
(3) polymer blend is added segmented copolymer as expanding material, improved the right consistency of polymkeric substance, reduced being separated, further improved Mechanical Properties of Materials.
(4) under the situation of conventional plasticized poly lactic acid, add polynite and strengthen, improving the loss of having avoided intensity under the flexible situation greatly, carry out toughness reinforcing matrix material with the use polymkeric substance and contrast, show similar excellent properties.
(5) prepared matrix material is compared with pure poly(lactic acid), tensile strength near or surpass under the situation of pure poly(lactic acid), elongation at break obviously improves, Young's modulus obviously increases.The tensile strength maximum has improved 21%, and the Young's modulus maximum has improved 74%, and the elongation at break maximum has improved 277%.
Embodiment
The preparation method of the modified organo montmorillonite that the present invention adopts is:
1. Na polynite and alkylamine are pressed 100: the mass ratio of 1-5, be dispersed in 70～90 ℃ of deionized waters, and the mass percent concentration that makes the Na polynite continued vigorous stirring 3～5 hours less than 8%; After filtration, the washing back is standby;
2. under 70～90 ℃, following component is mixed by following mass percent, refluxed again 3～5 hours; Through suction filtration, behind the deionized water wash,, after grinding, 100～300 purpose sieve get modified organo montmorillonite 100～105 ℃ of oven dry down; Component utilized and mass percent are:
Through step a gained modified montmorillonoid 5～20%,
80%～95% aqueous ethanolic solution 70～95%,
Silane coupling agent 1～5%,
0.1mol/L concentrated hydrochloric acid 0.01～0.05%.
Embodiment 1: 100 parts of vacuum drying pure poly(lactic acid) are in torque rheometer, and at 140～210 ℃, rotating speed is to carry out melt-processed 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plates in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 2: 89 parts of vacuum drying polylactic acid PLAs, after 1 part of mixing of 10 parts of PCL and common organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 3: 89 parts of vacuum drying polylactic acid PLAs, after 1 part of mixing of 10 parts of PCL and TFC organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 4: 89 parts of vacuum drying polylactic acid PLAs, after 1 part of mixing of 10 parts of expanding material PLA-PCL-PLA segmented copolymers and common organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 5: 89 parts of vacuum drying poly(lactic acid), after 1 part of mixing of 10 parts of expanding material PLA-PCL-PLA segmented copolymers and TFC organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 6: 89 parts of vacuum drying polylactic acid PLAs, 7 parts of PCL, after 1 part of mixing of 3 parts of expanding material PLA-PCL-PLA segmented copolymers and common organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 7: 89 parts of vacuum drying polylactic acid PLAs, 7 parts of PCL, after 1 part of mixing of 3 parts of expanding material PLA-PCL-PLA segmented copolymers and TFC organic modification montmonrillonite in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 8: 89 parts of vacuum drying polylactic acid PLAs, 10 parts of TEC, after 0.002 part in 1 part of common organic modification montmonrillonite and lubricant stearic acid aluminium and 0.006 part of mixing of thermo-stabilizer MALEIC ANHYDRIDE in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 9: 89 parts of vacuum drying polylactic acid PLAs, 10 parts of TEC, after 0.002 part in 1 part of TFC organic modification montmonrillonite and lubricant stearic acid aluminium and 0.006 part of mixing of thermo-stabilizer MALEIC ANHYDRIDE in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 10: 89 parts of vacuum drying polylactic acid PLAs, 10 parts of ATBC, after 0.002 part in 1 part of common organic modification montmonrillonite and lubricant stearic acid aluminium and 0.006 part of mixing of thermo-stabilizer MALEIC ANHYDRIDE in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Embodiment 11: 89 parts of vacuum drying polylactic acid PLAs, 10 parts of ATBC, after 0.002 part in 1 part of TFC organic modification montmonrillonite and lubricant stearic acid aluminium and 0.006 part of mixing of thermo-stabilizer MALEIC ANHYDRIDE in torque rheometer, at 140～210 ℃, rotating speed is to carry out melt blending intercalation 7～20min under 20～100rpm condition, and 140 ℃～210 ℃ hot pressing 5-20min become thin plate in heat pressing forming machines then.Its performance sees Table 1.
Table 1 polylactic acid blend/organic modification montmonrillonite nano composite material performance
| Example | Tensile strength (MPa) | Young's modulus (MPa) | Elongation at break (MPa) |
| 1 | 58.36 | 1701.73 | 5.47 |
| 2 | 48.56 | 1518.08 | 12.84 |
| 3 | 49.59 | 1623.68 | 13.39 |
| 4 | 67.21 | 2528.17 | 3.38 |
| 5 | 70.35 | 2957.30 | 4.01 |
| 6 | 57.99 | 2472.89 | 6.39 |
| 7 | 58.20 | 2616.98 | 8.79 |
| 8 | 50.33 | 2422.68 | 10.34 |
| 9 | 54.79 | 2718.84 | 13.01 |
| 10 | 54.93 | 2541.83 | 16.74 |
| 11 | 59.53 | 2774.74 | 20.64 |
Claims (4)
1. toughness reinforcing enhancing poly lactic acid nano composite material is characterized in that having used the modified organo montmorillonite TFC (Twice Functionalized Clay) of secondary functionization, and the composition of this matrix material and quality percentage composition are:
Poly(lactic acid) 60～90% toughner 5～20%
1～20 part of thermo-stabilizer 0～0.1% of expanding material
1～10 part of lubricant 0～0.1% of modified organo montmorillonite;
Wherein, described modified organo montmorillonite prepares as follows:
A. Na polynite and alkylamine are pressed 100: the mass ratio of 1-5, be dispersed in 70～90 ℃ of deionized waters, and the mass percent concentration that makes the Na polynite continued vigorous stirring 3～5 hours less than 8%; After filtration, the washing back is standby;
B. under 70～90 ℃, following component is mixed by following mass percent, refluxed again 3～5 hours; Through suction filtration, behind the deionized water wash,, get modified organo montmorillonite after the grinding of sieving 100～105 ℃ of oven dry down; Component utilized and mass percent are:
Through step a gained modified montmorillonoid 5～20%,
80%～95% aqueous ethanolic solution 70～95%,
Silane coupling agent 1～5%,
0.1mol/L concentrated hydrochloric acid 0.01～0.05%.
2. toughness reinforcing enhancing poly lactic acid nano composite material according to claim 1, the viscosity-average molecular weight that it is characterized in that described poly(lactic acid) is 150～4,000,000, and glass temperature range is 40～60 ℃, and the melt temperature scope is 150～210 ℃; Described toughner is: biodegradable polymers class or softening agent class; Described expanding material comprises: PLA-PCL-PLA, PLA-PEO-PLA, PLA-PHB-PLA, PLA-PGA-PLA, any one or two kinds of above segmented copolymers among the PLA-PE0-PLA; Described alkylamine is organically-modified cationite; Described silane coupling agent is a gamma-amino propyl-triethylsilicane oxygen alkane (KH-550), γ-glycidyl ether propyl trimethoxy silicane (KH-560), 3-(2-aminoethyl)-aminopropyl methyl dimethoxysilane (SCA-602), one or several in the vinyltriethoxysilane (A-151); Described thermo-stabilizer is MALEIC ANHYDRIDE or epoxy soybean oil; Described lubricant is aluminum stearate or calcium stearate.
3. toughness reinforcing enhancing poly lactic acid nano composite material according to claim 2 is characterized in that described biodegradable polymers class toughner is: poly-(6-caprolactone), polyoxyethylene, poly-hydroxy fatty acid butyl ester, polyglycolic acid, molecular weight are any one or two kinds of above mixtures in 300～4000 the polyoxyethylene glycol; Described softening agent class toughner is: any one or two kinds of above mixtures in ATBC, tri-n-butyl citrate, triethyl citrate, dioctyl phthalate (DOP), the dibutyl phthalate; Described organically-modified cationite is: heptadecyl carboxyl ammonium chloride, octadecyl ammonium chloride, octadecyl double hydroxyethyl ammonio methacrylate, a kind of or mixture more than two kinds in the distearyl dimethyl ammonium chloride.
4. the preparation method of a toughness reinforcing enhancing poly lactic acid nano composite material according to claim 1 is characterized in that the concrete steps of this method are:
A. Na polynite and alkylamine are pressed 100: the mass ratio of 1-5, be dispersed in 70～90 ℃ of deionized waters, and the mass percent concentration that makes the Na polynite continued vigorous stirring 3～5 hours less than 8%; After filtration, the washing back is standby;
B. under 70～90 ℃, following component is mixed by following mass percent, refluxed again 3～5 hours; Through suction filtration, behind the deionized water wash,, after grinding, 100～300 purpose sieve get modified organo montmorillonite 100～105 ℃ of oven dry down; Component utilized and mass percent are:
Through step a gained modified montmorillonoid 5～20%,
80%～95% aqueous ethanolic solution 70～95%,
Silane coupling agent 1～5%,
0.1mol/L concentrated hydrochloric acid 0.01～0.05%;
C. strengthen the preparation of plasticizing polylactic acid nano composite material: according to the component and the proportioning of above-mentioned matrix material, use torque rheometer at 140～210 ℃, rotating speed is to carry out the melt blending intercalation under 20～50rpm condition 3～6 minutes, and then be to carry out melt blending intercalation 3～6min under 50～100rpm condition at rotating speed, coldmoulding 8～20 minutes, be incubated 1～5 hour down at 100～110 ℃ at last, the plasticizing polylactic acid nano composite material promptly is enhanced.
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| CN102212258A (en) * | 2011-04-29 | 2011-10-12 | 永康市南益生物科技有限公司 | Modified poly(lactic acid) masterbatch prepared from poly(lactic acid) residual material or waste material and application thereof |
| CN102268178A (en) * | 2011-05-27 | 2011-12-07 | 东华大学 | Transparent plasticized polylactic acid nano resin slice with low mobility and preparation method thereof |
| CN103788602A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Highly heat-resistant and rapidly crystallized polylactic acid resin, and preparation method thereof |
| CN105462199A (en) * | 2015-12-16 | 2016-04-06 | 无锡吉进环保科技有限公司 | Environment-friendly plastic |
| JP2017179234A (en) * | 2016-03-31 | 2017-10-05 | 株式会社カネカ | Resin composition and medical tubular body |
| CN108130002A (en) * | 2017-12-29 | 2018-06-08 | 中山荣思东数码科技有限公司 | A kind of biodegradable hot melt adhesive and preparation method thereof |
| CN109320927A (en) * | 2018-07-19 | 2019-02-12 | 浙江田成环境科技有限公司 | A kind of lactic acid composite material and its manufacturing method |
| CN111607255A (en) * | 2020-06-09 | 2020-09-01 | 新疆大学 | Polylactic acid-modified vermiculite composite material, preparation method and application |
| CN112608585A (en) * | 2020-12-10 | 2021-04-06 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN112608585B (en) * | 2020-12-10 | 2022-12-30 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| WO2024076749A1 (en) * | 2022-10-07 | 2024-04-11 | Jabil Inc. | Compostable composition |
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