CN103665799A - Polylactic acid/polyethylene glycol/carbon nano tube composite material and preparation method thereof - Google Patents
Polylactic acid/polyethylene glycol/carbon nano tube composite material and preparation method thereof Download PDFInfo
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- CN103665799A CN103665799A CN201210335447.5A CN201210335447A CN103665799A CN 103665799 A CN103665799 A CN 103665799A CN 201210335447 A CN201210335447 A CN 201210335447A CN 103665799 A CN103665799 A CN 103665799A
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- carbon nano
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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Abstract
The invention belongs to the technical field of a high polymer material and relates to a polylactic acid/polyethylene glycol/carbon nano tube composite material and a preparation method thereof. The polylactic acid/polyethylene glycol/carbon nano tube composite material is prepared from the following components in parts by weight: 100 parts of polylactic acid. 1-5 parts of modified carbon nano tube, 10-50 parts of polyethylene glycol and 0.3-1.5 parts of antioxidant. Compared with the prior art, the dispersibility of the carbon nano tube in the polylactic acid is improved. The carbon nanot tube is added to the polylactic acid, so that the tensile strength and the impact resistance of the composite material can be improved; the carbon nano tube also can play a role in heterogeneous nucleation; crystallization of the polylactic acid is facilitated; the thermal stability is enhanced. The composite material prepared by the method has good mechanical property, tenacity and thermal stability.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA), as a kind of physiologically acceptable and degradable thermoplasticity aliphatics polyester, has high strength, high-modulus, the advantages such as low-carbon environment-friendly.Be widely used in packing, agricultural film, the fields such as bio-medical material, are considered as most possibly replacing the Biodegradable material of petroleum-type product by people.But poly(lactic acid) (PLA) crystallization velocity is slow, cause converted products insufficient strength high, resistance toheat is poor; In addition, the poor toughness of poly(lactic acid) (PLA), is a kind of hard and crisp material at normal temperatures, has limited significantly the application of PLA.For the problems referred to above, people by adding filler in poly(lactic acid), and elastomerics etc. improve the performance of poly(lactic acid), expand its range of application, have great importance.
Carbon nanotube be by single or multiple lift graphite flake around central shaft by the curling seamless nano level pipe forming of certain helix angle.Not only there is low density, high strength, high-modulus, high length-diameter ratio, unique advantages such as conductivity, also have good resistance to elevated temperatures, are a kind of desirable packing materials.Research shows, adds a certain amount of carbon nanotube and can effectively improve poly(lactic acid) mechanical property, the correlated performances such as resistance toheat in poly(lactic acid).Wherein, the dispersion of carbon nanotube in polymkeric substance and the performance of matrix material is had to considerable influence with the interaction of polymer interface, therefore, can first carry out corresponding modification to carbon nanotube, then carry out compound with poly(lactic acid).
For further improving the toughness of poly(lactic acid), can in lactic acid composite material, introduce polyoxyethylene glycol (PEG), preparation toughness and the good lactic acid composite material that can be applicable to injection raw material of resistance toheat.
Summary of the invention
The object of the invention is to provides a kind of poly(lactic acid)/poly ethyldiol modified carbon nano tube compound material and preparation method thereof for overcoming the defect of prior art.The present invention selects through the carbon nanotube of modification and elastomerics, prepares poly(lactic acid)/polyoxyethylene glycol/modified carbon nano-tube matrix material that thermal stability and toughness etc. all improve a lot.
For achieving the above object, the technical solution used in the present invention is as follows:
Poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material, by the component that comprises following weight part, made:
100 parts of poly(lactic acid),
1 ~ 5 part of modified carbon nano-tube,
Polyoxyethylene glycol (PEG) 10-50 part,
0.3 ~ 1.5 part, oxidation inhibitor.
The weight-average molecular weight of described poly(lactic acid) is 5 ~ 400,000.
Described polyoxyethylene glycol (PEG) molecular weight is 200 ~ 20000.
Described modified carbon nano-tube is that carbon nanotube is joined to ultrasonic 25 ~ 50min in the mixing solutions of concentrated acid and potassium permanganate, with filter membrane suction filtration, is washed with distilled water to neutrality, obtains the carbon nanotube of acidifying after vacuum-drying; Then the carbon nanotube of acidifying and maleic anhydride are added in the mixed solution of concentrated hydrochloric acid and ethyl acetate, ultrasonic 25min ~ 50min, mechanical stirring 3 ~ 6h under room temperature, with filter membrane suction filtration, with ethanol and distilled water repetitive scrubbing, to neutral, after vacuum-drying, obtain the carbon nanotube of grafted maleic anhydride.
Described carbon nanotube is multi-walled carbon nano-tubes, and its external diameter is 15 ~ 25nm, and internal diameter is 4 ~ 9nm, and purity is greater than 95wt%.
Described concentrated acid and the mixing solutions of potassium permanganate are dense H
2sO
4, dense H
3pO
4and KMnO
4mixing solutions, dense H wherein
2sO
4with dense H
3pO
4volume ratio is 2:1, KMnO
4massfraction be 0.3% of potassium permanganate and the vitriol oil, strong phosphoric acid mixing solutions.
The carbon nanotube of described acidifying and the mass ratio of maleic anhydride are 1:6; Concentrated hydrochloric acid and ethyl acetate volume ratio are 1:40, and the volume ratio of the mixed solution of the quality of carbon nanotube and concentrated hydrochloric acid and ethyl acetate is 1:135.
The concentration of the described vitriol oil is 18.4mol/L, and the concentration of concentrated hydrochloric acid is 12mol/L, and the concentration of strong phosphoric acid is 14.63mol/L.
Described oxidation inhibitor is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid ester three (2,4-di-tert-butyl phenyl) dimer of ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl), pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, many alkyl dihydroxyphenyl propane phosphorous acid ester or one or more in tripolymer.
A preparation method for above-mentioned poly(lactic acid)/poly ethyldiol modified carbon nano tube compound material, comprises following steps:
(1) according to said ratio, taking weight part is the poly(lactic acid) of 100 parts, 1 ~ 5 part of modified carbon nano-tube, and 10 ~ 50 parts of PEG, 0.3-1.5 part oxidation inhibitor mixes in mixing machine;
(2) mixture twin screw extruder melt blending step (1) being obtained.
In described step (2), extrusion temperature is 150 ℃ ~ 210 ℃, and the screw speed of twin screw extruder is 50 ~ 100rpm.
The present invention compared with the existing technology, has the following advantages and beneficial effect:
(1) the present invention adopts certain method of modifying, at the certain polar group of carbon nano tube surface grafting, has effectively strengthened the interaction between poly(lactic acid) and carbon nanotube, has improved the dispersiveness of carbon nanotube in poly(lactic acid);
(2) the present invention adds carbon nanotube in poly(lactic acid), not only can improve tensile strength and the shock strength of matrix material, and carbon nanotube can also play the effect of heterogeneous nucleation, promotes poly(lactic acid) crystallization, strengthens its thermal stability;
(3) adding not only as softening agent of elastomerics PEG, also can increase the toughness of lactic acid composite material;
(4) the present invention utilizes simple preparation technology, can obtain and have excellent mechanical performances, the lactic acid composite material of toughness and thermal stability.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
The preparation method of modified carbon nano-tube in the following example:
Carbon nanotube is joined to dense H
2sO
4, dense H
3pO
4, KMnO
4mixing solutions in (dense H wherein
2sO
4with dense H
3pO
4volume ratio is 2:1, KMnO
4massfraction be whole solution 0.3%), ultrasonic 25 ~ 50min, with filter membrane suction filtration, repeatedly to neutral, obtains the carbon nanotube of acidifying with distilled water repetitive scrubbing after vacuum-drying;
Carbon nanotube after acidifying and a certain amount of maleic anhydride are added in the mixed solution of concentrated hydrochloric acid and ethyl acetate, (wherein the mass ratio of carbon nanotube and maleic anhydride is 1:6; Concentrated hydrochloric acid and ethyl acetate volume ratio are 1:40, ultrasonic 25min ~ 50min, and mechanical stirring 3 ~ 6h under room temperature, with filter membrane suction filtration, uses ethanol and distilled water repetitive scrubbing to neutral, obtains the carbon nanotube of grafted maleic anhydride after vacuum-drying, standby.Wherein the volume ratio of the mixed solution of the quality of carbon nanotube and concentrated hydrochloric acid and ethyl acetate is 1:135.
Embodiment 1
By 100 parts of poly(lactic acid), 1 part of standby modified carbon nano-tube, 10 parts of PEG and 0.3 part of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester mixes in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, and screw speed is 50 ~ 100rpm, make lactic acid composite material, its performance is in Table 1.
Embodiment 2
By 100 parts of poly(lactic acid), 1.5 parts of modified carbon nano-tubes, 15 parts of PEG and 0.5 part of phosphorous acid ester three (2,4-di-tert-butyl phenyl) ester mixes in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, and screw speed is 50 ~ 100rpm, make lactic acid composite material, its performance is in Table 1.
Embodiment 3
By 100 parts of poly(lactic acid), 2 parts of modified carbon nano-tubes, 20 parts of PEG and 0.7 part of phosphorous acid benzene two isodecyl ester mix in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, and screw speed is 50 ~ 100rpm, make lactic acid composite material, its performance is in Table 1.
Embodiment 4
By 100 parts of poly(lactic acid), 2.5 parts of modified carbon nano-tubes, 25 parts of PEG and 0.9 part of three (nonyl is for phenyl) phosphorous acid ester mix in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, screw speed is 50 ~ 100rpm, makes lactic acid composite material, and its performance is in Table 1.
Embodiment 5
By 100 parts of poly(lactic acid), 3 parts of modified carbon nano-tubes, 30 parts of PEG and 1.1 parts of tricresyl phosphites (nonyl phenyl) mix in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, screw speed is 50 ~ 100rpm, makes lactic acid composite material, and its performance is in Table 1.
Embodiment 6
By 100 parts of poly(lactic acid), 3.5 parts of modified carbon nano-tubes, 35 parts of PEG and 1.2 parts of pentaerythritol bis-phosphites two (2,4-di-tert-butyl phenyl) ester mixes in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, and screw speed is 50 ~ 100rpm, make lactic acid composite material, its performance is in Table 1.
Embodiment 7
By 100 parts of poly(lactic acid), 4 parts of modified carbon nano-tubes, the dimer of 45 parts of PEG and the phosphorous acid ester of alkyl dihydroxyphenyl propane more than 1.3 parts mixes in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, screw speed is 50 ~ 100rpm, makes lactic acid composite material, and its performance is in Table 1.
Embodiment 8
By 100 parts of poly(lactic acid), 5 parts of modified carbon nano-tubes, the tripolymer of 50 parts of PEG and the phosphorous acid ester of alkyl dihydroxyphenyl propane more than 1.5 parts mixes in mixing machine, mixing with twin screw extruder, extrusion temperature is 150 ℃ ~ 210 ℃, screw speed is 50 ~ 100rpm, makes lactic acid composite material, and its performance is in Table 1.
Table 1
As can be seen from Table 1, along with modified carbon nano-tube, elastomerics PEG adds, the Young's modulus of lactic acid composite material, tensile strength, elongation at break and heat-drawn wire have raising in various degree, poly(lactic acid) toughness wherein, the defect that heat-drawn wire is low is greatly improved; From table, it can also be seen that, carbon nanotube has good enhancement, and meanwhile, when content of carbon nanotubes is higher, tensile strength changes not obvious, illustrates that carbon nanotube enhancement has saturated effect.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material, is characterized in that: by the component that comprises following weight part, made:
100 parts of poly(lactic acid),
1 ~ 5 part of modified carbon nano-tube,
Polyoxyethylene glycol 10-50 part,
0.3 ~ 1.5 part, oxidation inhibitor.
2. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 1, is characterized in that: the weight-average molecular weight of described poly(lactic acid) is 5 ~ 400,000.
3. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 1, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200 ~ 20000.
4. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 1, it is characterized in that: described modified carbon nano-tube is that carbon nanotube is joined to ultrasonic 25 ~ 50min in the mixing solutions of concentrated acid and potassium permanganate, with filter membrane suction filtration, be washed with distilled water to neutrality, after vacuum-drying, obtain the carbon nanotube of acidifying; Then the carbon nanotube of acidifying and maleic anhydride are added in the mixed solution of concentrated hydrochloric acid and ethyl acetate, ultrasonic 25min ~ 50min, mechanical stirring 3 ~ 6h under room temperature, with filter membrane suction filtration, with ethanol and distilled water repetitive scrubbing, to neutral, after vacuum-drying, obtain the carbon nanotube of grafted maleic anhydride.
5. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 4, is characterized in that: described carbon nanotube is multi-walled carbon nano-tubes, and its external diameter is 15 ~ 25nm, and internal diameter is 4 ~ 9nm, and purity is greater than 95wt%.
6. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 4, is characterized in that: described concentrated acid and the mixing solutions of potassium permanganate are dense H
2sO
4, dense H
3pO
4and KMnO
4mixing solutions, dense H wherein
2sO
4with dense H
3pO
4volume ratio is 2:1, KMnO
4massfraction be 0.3% of potassium permanganate and the vitriol oil, strong phosphoric acid mixing solutions.
7. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 4, is characterized in that: the carbon nanotube of described acidifying and the mass ratio of maleic anhydride are 1:6; Concentrated hydrochloric acid and ethyl acetate volume ratio are 1:40, and the volume ratio of the mixed solution of the quality of carbon nanotube and concentrated hydrochloric acid and ethyl acetate is 1:135.
8. poly(lactic acid)/polyoxyethylene glycol/carbon nano tube compound material according to claim 1, it is characterized in that: described oxidation inhibitor is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid ester three (2,4-di-tert-butyl phenyl) dimer of ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl), pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, many alkyl dihydroxyphenyl propane phosphorous acid ester or one or more in tripolymer.
9. according to the preparation method of arbitrary described poly(lactic acid)/poly ethyldiol modified carbon nano tube compound material in claim 1-8, it is characterized in that: comprise following steps:
(1) according to proportioning claimed in claim 1, taking weight part is the poly(lactic acid) of 100 parts, 1 ~ 5 part of modified carbon nano-tube, and 10 ~ 50 parts of polyoxyethylene glycol, 0.3-1.5 part oxidation inhibitor mixes in mixing machine;
(2) mixture twin screw extruder melt blending step (1) being obtained.
10. preparation method according to claim 9, is characterized in that: in described step (2), extrusion temperature is 150 ℃ ~ 210 ℃, and the screw speed of twin screw extruder is 50 ~ 100rpm.
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|---|---|---|---|
| CN201210335447.5A CN103665799A (en) | 2012-09-12 | 2012-09-12 | Polylactic acid/polyethylene glycol/carbon nano tube composite material and preparation method thereof |
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|---|---|---|---|---|
| CN104072834A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and carbon nano tube filled emulsion coprecipitated rubber and preparation method thereof |
| CN105199339A (en) * | 2015-10-19 | 2015-12-30 | 福建师范大学 | PBS (poly butylenes succinate)/PBAT (poly butyleneadipate-co-terephthalate)/CNTs (Carbon Nanotubes) material for 3D printing and preparation method of PBS/PBAT/CNTs material |
| CN105400118A (en) * | 2015-12-18 | 2016-03-16 | 南京林业大学 | Carbon nanotube modified 3D printing wire rod and preparation method thereof |
| CN106280326A (en) * | 2015-06-03 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of lactic acid composite material and preparation method and application |
| CN107987497A (en) * | 2017-12-22 | 2018-05-04 | 衢州听语信息科技有限公司 | A kind of 3D printing material |
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| CN112175364A (en) * | 2020-09-24 | 2021-01-05 | 天津全和诚科技有限责任公司 | High-performance composite material for medical use and preparation method thereof |
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| CN104072834A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and carbon nano tube filled emulsion coprecipitated rubber and preparation method thereof |
| CN104072834B (en) * | 2014-06-27 | 2016-02-03 | 青岛大学 | One is oil-filled fills carbon nanotube latex coprecipitation rubber and preparation method thereof |
| CN106280326A (en) * | 2015-06-03 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of lactic acid composite material and preparation method and application |
| CN105199339A (en) * | 2015-10-19 | 2015-12-30 | 福建师范大学 | PBS (poly butylenes succinate)/PBAT (poly butyleneadipate-co-terephthalate)/CNTs (Carbon Nanotubes) material for 3D printing and preparation method of PBS/PBAT/CNTs material |
| CN105400118A (en) * | 2015-12-18 | 2016-03-16 | 南京林业大学 | Carbon nanotube modified 3D printing wire rod and preparation method thereof |
| CN105400118B (en) * | 2015-12-18 | 2018-06-26 | 南京林业大学 | A kind of carbon nano-tube modification 3D printing wire rod and preparation method thereof |
| US10647057B2 (en) | 2016-07-20 | 2020-05-12 | Polyvalor, Limited Partnership | Electrically conductive ink for solvent-cast 3D printing |
| CN107987497A (en) * | 2017-12-22 | 2018-05-04 | 衢州听语信息科技有限公司 | A kind of 3D printing material |
| CN108912276A (en) * | 2018-07-31 | 2018-11-30 | 哈工大（威海）创新创业园有限责任公司 | A kind of heterogeneous ion-exchange membrane material of biocompatibility and preparation method thereof |
| CN108912276B (en) * | 2018-07-31 | 2020-09-18 | 哈工大（威海）创新创业园有限责任公司 | Biocompatible heterogeneous ion exchange membrane material and preparation method thereof |
| CN109265944A (en) * | 2018-09-05 | 2019-01-25 | 南京林业大学 | A kind of preparation method of high intensity antibacterial carbon nano tube/silver/lactic acid composite material |
| CN112175364A (en) * | 2020-09-24 | 2021-01-05 | 天津全和诚科技有限责任公司 | High-performance composite material for medical use and preparation method thereof |
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Application publication date: 20140326 |