CN102719070A - Preparation process of novel poly propylene carbonate nano-composite - Google Patents
Preparation process of novel poly propylene carbonate nano-composite Download PDFInfo
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Abstract
The invention discloses a preparation process of a novel poly propylene carbonate (PPC) nano-composite. The composite is prepared by taking functionalized graphite and carbon nanotubes as packing, taking degradable PPC polymer as a matrix and then fusing or mixing in solution. The preparation process includes steps (1), synthesis and surface treatment of functionalized packing: oxidizing the packing by strong oxidizers and then enabling the packing to react with isocyanate and polyatomic alcohol to obtain the functionalized packing; and (2), preparation of PPC-matrix composite: mixing the functionalized packing with polymer in solution or by means of fusing. By the preparation process, dispersion effect of the packing can be improved, interface bonding strength of the packing and the matrix can be improved, and mechanical and thermal performance of the composition can be improved. The composite prepared by the preparation process is excellent in performance and low-cost and is a full-degradable environment-friendly material, and further, the applicable range of PPC is expanded effectively and good application prospect can be achieved.
Description
Technical field
The present invention relates to modified polymethyl ethylene carbonate material, in particular to a kind of preparation method of novel lined polymethyl ethylene carbonate nano composite material.
Background technology
At present, environmental issue has caused countries in the world concern more and more widely, and the researchist is exploring about how solving the problem of " white pollution " that caused by nondegradable macromolecular material waste.Filler is one of important additives of polymer composites, and in polymeric matrix, adding filler is the important means of improving the polymer materials performance.Filler not only can reduce the cost of matrix material, can also improve some physics or the chemical property of polymer composites simultaneously.The kind of filler is a lot, because of the difference of its The Nomenclature Composition and Structure of Complexes, has different physics and chemical property, thereby has different filling effects.
In recent years, how to separate efficiently, reclaim and utilize carbonic acid gas (CO
2) become the problem that comes into one's own day by day in the world wide.Especially utilizing the synthetic complete degradable plastic of carbonic acid gas is present worldwide research focus, and it is the effective way that alleviates " Greenhouse effect " and solve " white pollution ".The aboveground auspicious flat discovery of Kyoto University in 1969 can be a complete degradable plastic with carbon dioxide fixation; The Air Products and Chemicals of the U.S.; Inc. (air products company) through after buying Japanese Patent and applying for the USP of improved catalyst, the commodity selling of existing carbon dioxide copolymer in 1994.Current, Japan has formed the throughput of producing 3000～4000 tons of carbon dioxide copolymers per year, but the processing characteristics of gained multipolymer, mechanics and thermal property are not good enough, remains further to be improved.
Lined polymethyl ethylene carbonate (PPC) is the degradable high polymer material that under certain catalyst action, is obtained through anionic coordinate polymerization by carbonic acid gas and propylene oxide.Utilize C0
2The synthesis and degradation plastics, raw material sources are abundant, cheap, and elongation at break is high, and is transparent, has light, biological degradation function again concurrently; But poor mechanical property is to thermo-responsive.For widening its Application Areas; In recent years; It is the research of degradable plastics modification that China has carried out carbon dioxide fixation in succession, and it is the research of degradable plastics that scientific research institutions such as China Chinese Academy of Sciences, Zhejiang University, Lanzhou University and Zhongshan University have carried out carbon dioxide fixation in succession, has studied the relation of carbonic acid gas complete degradable plastic structure and performance comprehensively; To the relatively poor relatively shortcoming of carbonic acid gas complete degradable plastic thermostability; Developed and improved the technical recipe and the heat processing technique of carbonic acid gas complete degradable plastic thermostability, and carried out carbonic acid gas complete degradable plastic blending and modifying and foaming formulation and technical study, obtained the experimental data of abundant practicality.No matter be aspect polymerization, still aspect processed and applied, all formed the independent intellectual property rights of oneself, so far, obtained multinomial Chinese invention patent mandate and U.S.'s invention patent mandate, obtaining remarkable progress aspect the research of polymer performance and the modification.
The main means of modification comprise chemical graft-copolymerization method, polymkeric substance-polymer blending modification method, polyalcohol-filling material blending and modifying or the like.Wherein, adding filler is a kind of simple effective method.Filler commonly used is as having globular lime carbonate, carbonic acid gas, polynite etc. and have acicular thomel or the like.
Summary of the invention
The lined polymethyl ethylene carbonate based composites that the object of the present invention is to provide a kind of polycomponent, can degrade fully with good mechanical property and resistance toheat.When improving composite property, reduced the production cost of matrix material.
Simultaneously, the present invention also aims to provide the preparation method of the polymer matrix composite that can degrade fully, to simplify technology, enlarging application range.
In order to achieve the above object, technical program of the present invention lies in adopting a kind of polymer matrix composite that can degrade fully.This matrix material is a filler with the nano graphite flakes or the nanotube of functionalization, is matrix with degradable lined polymethyl ethylene carbonate, makes through solution blending or melt blending.Wherein, the shared weight percentage of functionalization filler is 0.5-30%.The weight percentage of described lined polymethyl ethylene carbonate polymer is 99.5-70%.
In above-mentioned matrix material, said polymeric matrix be by carbonic acid gas and propylene oxide alternating copolymerization and product, its molecular-weight average is 20,000 to 200,000, its chemical structure is:
In above-mentioned matrix material, said weighting agent is nano oxidized graphite, expanded graphite, the carbon nanotube of functional modification.
In above-mentioned matrix material, the functional method of filler is earlier through isocyanate-modified, again through the polyvalent alcohol graft modification.
Said graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible black lead preparation; Step is following: in the presence of the vitriol oil, potassium permanganate and SODIUMNITRATE, in reacting 10 ~ 20min below 4 ℃, 35 ~ 38 ℃ are reacted 1 ~ 2h down with natural graphite powder, natural flake graphite or expansible black lead; React 1 ~ 2h down at 90 ~ 100 ℃ again; Product is with 5% hydrochloric acid and deionized water thorough washing, and dry 12 ~ 36h obtains the graphite oxide carrier in 60 ~ 90 ℃ of vacuum drying ovens.
Said carbon nanotube carrier is by single wall or multi-walled carbon nano-tubes preparation; Comprise the steps: SWCN or many walls nanotube in the presence of the vitriol oil and concentrated nitric acid; The volume ratio of the vitriol oil and concentrated nitric acid is 1:5 ~ 5:1, and in 80 ~ 120 ℃ of refluxed reaction 6 ~ 36h, product is used the deionized water thorough washing; At 60 ~ 90 ℃ of dry 12 ~ 36h of following vacuum-drying, obtain carbon nanotube carrier.
Said expanded graphite carrier is prepared by expansible black lead, comprises the steps: expansible black lead to obtain the expanded graphite carrier at 700 ~ 1000 ℃ of following puffing 5 ~ 30s.
The preparation method of said matrix material is solution blended process or scorification preparation.The solution blending preparation method; Comprise the steps: quantitative functionalization filler is added among the excessive DMF, ultra-sonic dispersion 0.5 ~ 5h is behind stirring at room 5 ~ 30min; Quantitative lined polymethyl ethylene carbonate (PPC) is added in the above-mentioned mixed system that contains filler; Behind 40 ~ 60 ℃ of following mechanical stirring 12-36h, pour mixed system in watch-glass room temperature vacuum-drying, obtain the matrix material of different filler contents.The melt blending preparation method; Comprise the steps: to require quantitative functionalization filler is added among the quantitative PPC, after mechanically mixing, mixture is added in the melting mixing equipment according to prescription; At 150 ~ 190 ℃; Rotating speed 20 ~ 100rpm, mixing time 3 ~ 10min carries out the matrix material that melt blending obtains different filler contents.
Simultaneously; Technical program of the present invention also lies in adopting a kind of preparation method of polymer composites of multi-component totally degradable; Employing is a filler through the graphite nano plate or the carbon nanotube of functional modification in advance; To be matrix, obtain through solution blending or melt blending by carbonic acid gas and propylene oxide synthetic degradable lined polymethyl ethylene carbonate polymer.
Because filler that the present invention adopted is the nano material through functional modification, filler homodisperse in matrix, and combine well with the interface of matrix polymer, be the key that obtains the good matrix material of mechanical property and thermal property.The present invention carries out oxide treatment with graphite or carbon nanotube earlier, introduces the polar oxy radical on its surface, these oxy radicals ability and isocyanate reactions, thus improved the dispersive ability of filler in solvent.The end functional group of isocyanic ester can react with a terminal hydroxy group of polyvalent alcohol simultaneously, and the other end hydroxyl then produces interaction of hydrogen bond with the lined polymethyl ethylene carbonate polymer matrix, is the middle bridge of bonding pad and polymeric matrix.The lined polymethyl ethylene carbonate polymer that the present invention adopts is a matrix; Lined polymethyl ethylene carbonate is the complete alternative multipolymer of carbonic acid gas and propylene oxide; The weight percentage of carbonic acid gas in its main chain is 43%, is a kind of macromolecular material with applications well prospect; With functional modification have the nanometer lamella or the piped filler is a weighting agent, solved scattering problem and the interface problem of Nano filling in the lined polymethyl ethylene carbonate polymer matrix, can the good multinomial matrix material of obtained performance.The present invention adopts that the source is abundant, cheap graphite or nanotube is filler, has overcome the binding deficient between filler and the matrix with the means of chemistry, has reduced production cost.Preparation technology of the present invention is simple; Use range is wide, and the net content of filler can be controlled in 0.5-30% in the product, has higher mechanical property and thermal property; The gained matrix material finally can be degraded fully, is a kind of environmental protection matrix material of novel Sustainable development.
Filler functionalization technology among the present invention is meant: earlier a certain amount of graphite oxide or carbon nanotube (2g) adding 250mL are contained in the three-necked bottle of 100mL dry DMF, after feeding nitrogen was removed air, ultra-sonic dispersion obtained uniform dispersion system.Again system is moved in the water-bath, add excessive isocyanic ester, in 80
oC lower magnetic force stirring reaction 24h adds excessive butyleneglycol afterwards again in 80
oC lower magnetic force stirring reaction 24h, last, in system, add the precipitation agent acetone product that settles out, and through centrifugally concentrate, washing with alcohol removes unreacted butyleneglycol.Products therefrom is 100
oVacuum-drying 48h under the C.
Compared with prior art, the present invention has following beneficial effect:
(1) used polymeric matrix of the present invention and filler raw material source is abundant, with low cost.
(2) composite material and preparation method thereof of the present invention is simple, and is easy to operate, practicality is wide.
(3) gained composite materials property of the present invention and thermal property are high.When satisfying performance requriements, the amount of required filler still less.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Accurately take by weighing the 10g natural graphite, under agitation slowly join and be cooled to 4 through ice-water bath
oIn the 230mL vitriol oil (98%) below the C, slowly add 5g SODIUMNITRATE and 28g potassium permanganate again, stirring reaction 10min.Remove ice bath, forward reaction system to 36
oIn the hot water bath of C behind the stirring reaction 30min, again in oil bath 95
oStirring reaction 1h under the C, product is with 5% hydrochloric acid and deionized water thorough washing, 90
oDry 24h in the C vacuum drying oven obtains the graphite oxide carrier.
Accurately take by weighing 2g graphite oxide adding 250mL and contain in the three-necked bottle of 100mL dry DMF, after feeding nitrogen was removed air, ultra-sonic dispersion obtained uniform dispersion system.Again system is moved in the water-bath, add excessive isocyanic ester, in 80
oC lower magnetic force stirring reaction 24h adds excessive butyleneglycol afterwards again in 80
oC lower magnetic force stirring reaction 24h, last, in system, add the precipitation agent acetone product that settles out, and concentrate through centrifugal, washing with alcohol is removed unreacted butyleneglycol.Products therefrom is 100
oVacuum-drying 48h is subsequent use under the C.
The graphite oxide filler of 0.25g functionalization is added among the excessive DMF, and ultra-sonic dispersion 0.5 ~ 5h behind stirring at room 5 ~ 30min, adds 50g PPC in the above-mentioned mixed system that contains filler, at 40-60
oUnder the C behind the mechanical stirring 12-36h, mixed system poured into room temperature vacuum-drying obtains matrix material in the watch-glass.The content of filler is 0.5%.
The composite material by adopting compression molding appearance compressing tablet of gained is by the standard sample preparation of ISO527-2 and carry out Mechanics Performance Testing (standard of DSC, the standard of TG).From table 1 can find out matrix material mechanical property (tensile strength-
T s) and thermostability (weightless 50% temperature-
T -50%And second-order transition temperature-
T g) when hanging down loading level, all be improved largely than body material lined polymethyl ethylene carbonate polymer, can satisfy the performance demands of various lives and industrial or agricultural disposable product, have wide range of applications.
Embodiment 2
The preparation method of filler and functional method be with embodiment 1, and the graphite oxide filler of 0.53g functionalization is added among the excessive DMF, after the blend identical with embodiment 1, obtains filler content and be 1% matrix material.The test condition of matrix material is with embodiment 1, and the result sees table 1.
Embodiment 3
The preparation method of filler and functional method are with embodiment 1, and filler content is 3%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 4
The preparation method of filler and functional method are with embodiment 1, and filler content is 5%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 5
The preparation method of filler and functional method are with embodiment 1, and filler content is 10%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 6
The preparation method of filler and functional method are with embodiment 1, and filler content is 15%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 7
The preparation method of filler and functional method are with embodiment 1, and filler content is 20%, and all the other test conditions are with embodiment 1, and the result sees table 1.
The preparation method of filler and functional method are with embodiment 1, and filler content is 30%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 9
In many walls of 5g nanotube, add the 30ml vitriol oil and 30ml concentrated nitric acid, in 90 ℃ of refluxed reactions 24 hours, product was used the deionized water thorough washing, dry 24 hours of 80 ℃ of following vacuum-dryings, obtained carbon nanotube carrier.
The functional method of many walls nanotube is with embodiment 1.
Many walls nanotube filler of 0.25g functionalization is added among the excessive DMF, and ultra-sonic dispersion 0.5 ~ 5h behind stirring at room 5 ~ 30min, adds 50g PPC in the above-mentioned mixed system that contains filler, at 40-60
oUnder the C behind the mechanical stirring 12-36h, mixed system poured into room temperature vacuum-drying obtains matrix material in the watch-glass.The content of filler is 0.5%.
All the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 10
The preparation method of filler and functional method are with embodiment 9, and filler content is 1%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 11
The preparation method of filler and functional method are with embodiment 9, and filler content is 3%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 12
The preparation method of filler and functional method are with embodiment 9, and filler content is 5%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 13
The preparation method of filler and functional method are with embodiment 9, and filler content is 10%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 14
The preparation method of filler and functional method are with embodiment 9, and filler content is 15%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 15
The preparation method of filler and functional method are with embodiment 9, and filler content is 20%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 16
Expansible black lead 900 ℃ of following puffings 10 seconds, is obtained expanded graphite packing.
The functional method of expanded graphite packing is with embodiment 1.
The expanded graphite packing of 0.53g functionalization is added among the excessive DMF, and ultra-sonic dispersion 0.5 ~ 5h behind stirring at room 5 ~ 30min, adds 50g PPC in the above-mentioned mixed system that contains filler, at 40-60
oUnder the C behind the mechanical stirring 12-36h, mixed system poured into room temperature vacuum-drying obtains matrix material in the watch-glass.The content of filler is 1%.
The preparation method of matrix material and test condition are with embodiment 1.The result sees table 1.
Embodiment 17
The preparation method of filler and functional method are with embodiment 16, and filler content is 5%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 18
The preparation method of filler and functional method are with embodiment 16, and filler content is 10%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 19
The preparation method of filler and functional method are with embodiment 16, and filler content is 20%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 20
The preparation method of filler and functional method are with embodiment 16, and filler content is 30%, and all the other test conditions are with embodiment 1, and the result sees table 1.
Embodiment 21
The preparation method of filler and functional method are with embodiment 1.
The graphite of 0.25g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 150 ℃, rotating speed 60 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 0.5% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 22
The preparation method of filler and functional method are with embodiment 1.
The graphite of 0.53g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 160 ℃, rotating speed 60 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 1% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 23
The preparation method of filler and functional method are with embodiment 1.
The graphite of 2.63g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 60 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 5% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 24
The preparation method of filler and functional method are with embodiment 1.
The graphite of 5.55g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 10% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 25
The preparation method of filler and functional method are with embodiment 1.
The graphite of 12.5g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 20% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 26
The preparation method of filler and functional method are with embodiment 9.
The 0.53g functionalized carbon nanotube is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 160 ℃, rotating speed 60 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 1% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 27
The preparation method of filler and functional method are with embodiment 9.
The 2.63g functionalized carbon nanotube is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 60 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 5% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 28
The preparation method of filler and functional method are with embodiment 9.
The 5.55g functionalized carbon nanotube is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 10% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 29
The preparation method of filler and functional method are with embodiment 9.
The 12.5g functionalized carbon nanotube is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 20% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 30
The preparation method of filler and functional method are with embodiment 16.
The expanded graphite of 0.53g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 60 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 1% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 31
The preparation method of filler and functional method are with embodiment 16.
The expanded graphite of 2.63g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 60 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 5% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 32
The preparation method of filler and functional method are with embodiment 16.
The 5.55g functionalized carbon nanotube is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 5 minutes, carrying out melt blending, to obtain filler content be 10% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
Embodiment 33
The preparation method of filler and functional method are with embodiment 16.
The expanded graphite of 12.5g functionalization is joined among the 30mLDMF, and the room temperature ultra-sonic dispersion obtains adding 50g PPC behind the uniform dispersion system, after mechanically mixing; Drying is removed solvent DMF; Mixture is added in the melting mixing equipment, at 170 ℃, rotating speed 70 rpm; Mixing time 10 minutes, carrying out melt blending, to obtain filler content be 20% matrix material.
The performance of composites test condition is with embodiment 1, and the result sees table 1.
The composition and performance of the matrix material among the present invention is as shown in the table:
The composition and the performance of table 1 lined polymethyl ethylene carbonate based composites
| Examples of implementation | Filler content (wt.%) | T s(MPa) | T g( oC) | T -50% ( oC) |
| Matrix | 0 | 14.1 | 28.1 | 240 |
| 1 | 0.5 | 17.7 | 32.4 | 305 |
| 2 | 1 | 21.9 | 36.3 | 322 |
| 3 | 3 | 29.5 | 41.9 | 344 |
| 4 | 5 | 27.7 | 41.6 | 338 |
| 5 | 10 | 23.2 | 42.2 | 340 |
| 6 | 15 | 22.1 | 42.7 | 346 |
| 7 | 20 | 18.1 | 43.1 | 349 |
| 8 | 30 | 16.8 | 43.4 | 353 |
| 9 | 0.5 | 18.4 | 33.7 | 324 |
| 10 | 1 | 22.7 | 38.4 | 337 |
| 11 | 3 | 31.8 | 42.1 | 345 |
| 12 | 5 | 33.9 | 43.3 | 359 |
| 13 | 10 | 28.3 | 44.1 | 366 |
| 14 | 15 | 24.1 | 44.7 | 372 |
| 15 | 30 | 16.2 | 44.7 | 389 |
| 16 | 1 | 15.9 | 33.8 | 316 |
| 17 | 5 | 21.2 | 35.9 | 326 |
| 18 | 10 | 24.1 | 37.6 | 346 |
| 19 | 20 | 25.3 | 40.1 | 357 |
| 20 | 30 | 18.6 | 41.7 | 366 |
| 21 | 0.5 | 15.8 | 33.3 | 277 |
| 22 | 1 | 18.1 | 37.1 | 292 |
| 23 | 5 | 21.1 | 38.2 | 312 |
| 24 | 10 | 22.7 | 40.6 | 336 |
| 25 | 20 | 16.5 | 40.2 | 342 |
| 26 | 1 | 19.7 | 38.3 | 312 |
| 27 | 5 | 23.1 | 41.2 | 334 |
| 28 | 10 | 22.4 | 42.6 | 351 |
| 29 | 20 | 16.5 | 43.9 | 375 |
| 30 | 1 | 15.9 | 35.2 | 286 |
| 31 | 5 | 18.2 | 38.0 | 302 |
| 32 | 10 | 23.5 | 40.1 | 322 |
| 33 | 20 | 16.2 | 42.3 | 342 |
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only; Although with reference to the foregoing description the present invention has been carried out detailed explanation, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention.Like classification to filler, the change of size etc., and do not break away from any modification or the local replacement of the spirit and scope of the present invention, all should cover within the claim scope of the present invention.
Description of drawings
The preparation flow of Fig. 1-new modified graphite oxide/PPC nano composite material is a representational preparation were established.
Claims (16)
1. lined polymethyl ethylene carbonate based composites; It is characterized in that: such matrix material is a filler with functionalized nano graphite flake or carbon nanotube; With degradable lined polymethyl ethylene carbonate polymer is matrix, makes through solution or melt-blending process, wherein; The shared weight percentage of functionalization filler is 0.5 ~ 30%, and the weight percentage of lined polymethyl ethylene carbonate polymer is 99.5 ~ 70%.
2. the polymer matrix composite that polycomponent according to claim 1 is degraded fully is characterized in that: described filler is graphite nano plate with nanostructure or carbon nanotube through functionalization.
3. the graphite of filler functional modification as claimed in claim 2 or carbon nanotube, wherein graphite is graphite oxide or expanded graphite, carbon nanotube is single (two) wall carbon nano tube.
4. filler as claimed in claim 3 is for to adopt strong oxidizer to carry out the graphite and the carbon nanotube of oxidation in advance.
5. strong oxidizer as claimed in claim 4 is the oxygenant that the vitriol oil, concentrated nitric acid, potassiumchromate, potassium permanganate etc. have strong oxidizing property.
6. graphite oxide as claimed in claim 3; It is characterized in that: said graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible black lead preparation; Step is following: natural graphite powder, natural flake graphite or expansible black lead in the presence of the vitriol oil, potassium permanganate and SODIUMNITRATE, are reacted 10 ~ 20 min under 4 ℃, 35～38 ℃ are reacted 1 ~ 2 h down; React 1 ~ 2 h down at 90 ~ 100 ℃ again; Product is with 5% hydrochloric acid and deionized water thorough washing, and dry 12 ~ 36 h obtain the graphite oxide carrier in 60 ~ 90 ℃ of vacuum drying ovens.
7. expanded graphite as claimed in claim 3 is characterized in that said expanded graphite carrier is prepared by expansible black lead, comprises the steps: expansible black lead to obtain the expanded graphite carrier at 700 ~ 1000 ℃ of following puffing 5 ~ 30 s.
8. carbon nanotube as claimed in claim 4; It is characterized in that said carbon nanotube is obtained by commercially available single wall or walled carbon nanotubes purification process; Comprise the steps: SWCN or many walls nanotube in the presence of strong oxidizing acid (like the vitriol oil or/and concentrated nitric acid); The volume ratio of the vitriol oil and concentrated nitric acid is 1:5 ~ 5:1, and in 80 ~ 120 ℃ of refluxed reaction 6 ~ 36 h, product is used the deionized water thorough washing; At 60 ~ 90 ℃ of dry 12 ~ 36 h of following vacuum-drying, obtain carbon nanotube.
9. graphite nano plate with nanostructure or carbon nanotube filler through functionalization according to claim 2 is characterized in that: graphite or carbon nanotube that processing is obtained obtain through the isocyanide ester reaction earlier.
10. graphite nano plate with nanostructure or carbon nanotube filler through functionalization according to claim 2 is characterized in that: with described functionalization graphite of claim 9 and carbon nanotube filler, obtain through polyol reaction again.
11. isocyanide ester according to claim 9 is a toluene diisocyanate.
12. polyvalent alcohol according to claim 9 is 1, the 4-butyleneglycol.
13. matrix material is characterized in that the shared weight percentage of described functionalization filler is 0.5 ~ 30% according to claim 1; The weight percentage of described lined polymethyl ethylene carbonate polymer is 99.5 ~ 70%.
14. the preparation method of matrix material is characterized in that adopting the preparation of solution blended process or scorification according to claim 1.
15. solution blending preparation method like the said matrix material of claim 13; Comprise the steps: quantitative functionalization filler is added among the excessive DMF, ultra-sonic dispersion 0.5 ~ 5 h is behind stirring at room 5 ~ 30 min; Quantitative lined polymethyl ethylene carbonate polymer is added in the above-mentioned mixed system that contains filler; Behind 40 ~ 60 ℃ of following mechanical stirring 12 ~ 36 h, pour mixed system in watch-glass room temperature vacuum-drying, obtain the matrix material of different filler contents.
16. melt blending preparation method like the said matrix material of claim 13; Comprise the steps: to require quantitative functionalization filler is added in the quantitative lined polymethyl ethylene carbonate polymer, after mechanically mixing, mixture is added in the melting mixing equipment according to prescription; At 150-190 ℃; Rotating speed 20-100 rpm, mixing time 3-10 min carries out the matrix material that melt blending obtains different filler contents.
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| CN108329808A (en) * | 2018-03-07 | 2018-07-27 | 常德金德新材料科技股份有限公司 | A kind of high barrier lined polymethyl ethylene carbonate/stannic oxide/graphene nano composite coating material |
| CN110746757A (en) * | 2019-10-31 | 2020-02-04 | 华中科技大学 | High-thermal-conductivity biodegradable polymer composite material and preparation method thereof |
| CN111065600A (en) * | 2017-10-30 | 2020-04-24 | 株式会社Lg化学 | Sulfur-carbon composite material and preparation method thereof |
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| J. BIAN ET AL.: "Preparation and characterization of modified graphite oxide/poly(propylene carbonate) composites by solution intercalation", 《POLYMER DEGRADATION AND STABILITY》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111065600A (en) * | 2017-10-30 | 2020-04-24 | 株式会社Lg化学 | Sulfur-carbon composite material and preparation method thereof |
| US20200152971A1 (en) * | 2017-10-30 | 2020-05-14 | Lg Chem, Ltd. | Sulfur-carbon composite and method for preparing same |
| US11611066B2 (en) * | 2017-10-30 | 2023-03-21 | Lg Energy Solution, Ltd. | Sulfur-carbon composite and method for preparing same |
| CN108329808A (en) * | 2018-03-07 | 2018-07-27 | 常德金德新材料科技股份有限公司 | A kind of high barrier lined polymethyl ethylene carbonate/stannic oxide/graphene nano composite coating material |
| CN110746757A (en) * | 2019-10-31 | 2020-02-04 | 华中科技大学 | High-thermal-conductivity biodegradable polymer composite material and preparation method thereof |
| CN110746757B (en) * | 2019-10-31 | 2021-03-16 | 华中科技大学 | High-thermal-conductivity biodegradable polymer composite material and preparation method thereof |
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