CN112094421B - Preparation method of modified reduced graphene oxide doped polylactic acid film - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 238000005266 casting Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention belongs to the technical field of cigarette processing, and provides a preparation method of a modified reduced graphene oxide doped polylactic acid film.
Description
Technical Field
The invention belongs to the technical field of cigarette processing, and particularly relates to a preparation method of a modified reduced graphene oxide doped polylactic acid film.
Background
The cigarette is heated without burning to generate smoke through cracking tobacco under the condition of 200-400 ℃ by an external heating element. Because the volume of the cigarette which is not burnt is relatively small, the cigarette is short, and the cigarette is not cooled by the unfired cigarette branch section and the filter stick which are similar to the traditional cigarette and have longer length, the adoption of the cooling filter stick to reduce the smoke temperature of the cigarette which is not burnt is a key technical measure for heating the cigarette which is not burnt at present.
The polylactic acid (PLA, ploy (lactic acid)) is prepared by refining, dehydrating, oligomerizing and polymerizing lactic acid prepared by using crops such as corn and the like as raw materials, has the characteristics of better biocompatibility, safety, no toxicity, easiness in processing and the like, and has better application prospect in a filter stick cooling section for heating non-burning cigarettes due to the lower phase transition temperature (55-60 oC). When the temperature of the flue gas is higher than the temperature, the polylactic acid material absorbs heat and generates phase change; however, when the temperature is lower than the phase transition temperature, the temperature lowering effect is suppressed, and the object is difficult to achieve. Therefore, the premise that the phase transition temperature is further reduced through polylactic acid modification design is that the polylactic acid is popularized and applied in the field of heating non-combustible cigarettes on a large scale. The Chinese patent CN109567271A discloses that alkyl ketene dimer and polylactic acid are copolymerized and the copolymer is attached to an inorganic carrier to be used as cooling particles to be added into a filter rod section, the cooling effect is better due to the addition uniformity of a cooling material, but the addition of the inorganic carrier reduces the stability of a phase-change material, has great influence on the smoking resistance of cigarettes and is easy to influence the smoking comfort. The chinese invention patent CN201911106368.5 discloses a polylactic acid film cooling material with nano-cage inorganic oxide hybrid cross-linking, but because the latent heat of phase change of the inorganic oxide is low, the cross-linking structure affects the mobility of the polymer chain segment, and the like, the cooling effect of the material in practical application is still to be verified.
The graphene has a high thermal conductivity coefficient, and is an ideal phase-change temperature regulator. However, as an inorganic material, graphene has poor compatibility with polylactic acid, which easily causes uneven dispersion in the polylactic acid film, thereby affecting the cooling effect of the polylactic acid film.
Disclosure of Invention
The invention aims to provide a preparation method of a modified Reduced Graphene Oxide doped polylactic acid film, aiming at the defects in the prior art, the invention takes polylactic acid as a main phase-change material, takes polylactic acid graft modified Reduced Graphene Oxide (rGO) as a phase-change temperature regulator, and adopts a solution casting film method to prepare the polylactic acid composite phase-change film material, thereby improving the cooling effect when the cigarette filter is not heated and combusted under the condition of not influencing the suction resistance and the suction comfort.
The object of the invention is achieved by the following technical measures.
The invention provides a preparation method of a modified reduced graphene oxide doped polylactic acid film, wherein the modified reduced graphene oxide doped in the film material is polylactic acid grafted reduced graphene oxide, and the preparation method comprises the following steps:
(1) Preparing benzophenone grafted modified reduced graphene oxide: under the protection of inert gas, dispersing 4-hydroxy-benzophenone (BP-OH) and rGO in a certain proportion into an organic solvent; adding a certain amount of potassium carbonate serving as a catalyst into the dispersion system, fully stirring, heating to boil, and reacting for a certain time under a reflux condition; and after the reaction is finished, cooling the temperature of a reaction system to room temperature, centrifugally separating rGO, fully washing with water to remove potassium carbonate, and freeze-drying to obtain the benzophenone grafted and modified rGO (rGO-BP).
The preferable mass ratio of BP-OH to rGO is 1: 1. 1 to a total of: 20; the preferred mass ratio of the potassium carbonate to the rGO is 1: 5.1 to a total of: 20; the organic solvent is preferably one of ethanol, normal propyl alcohol, isopropanol, glycol, acetonitrile, tetrahydrofuran and dioxane; the reflux reaction time is preferably 4 to 12 hours.
(2) Preparing polylactic acid grafted modified reduced graphene oxide: mixing PLA and rGO-BP in a certain proportion in a solvent and uniformly dispersing; and (3) placing the dispersion under an ultraviolet lamp for radiation grafting reaction for a certain time, centrifugally separating rGO, fully washing by using a solvent to remove ungrafted PLA, and freeze-drying to obtain PLA grafted rGO (rGO-PLA).
The preferable molecular weight of the PLA is 10000-300000 g/mol; the preferable mass ratio of PLA to rGO-BP is 1: 20. 1 to a total of: 1; the solvent is preferably water or an alcohol organic solvent capable of dissolving PLA; the radiation grafting reaction time is preferably 5 to 60 minutes; the ultraviolet light wavelength is preferably 365 nm.
(3) Preparing a modified reduced graphene oxide doped polylactic acid film: uniformly mixing rGO-PLA and PLA according to a certain proportion and dispersing the mixture into an organic solvent; the dispersion liquid is prepared into a film by solvent volatilization by adopting a solution casting method, and the obtained film is subjected to vacuum treatment at 80 ℃ for a certain time, so that the modified reduced graphene oxide doped polylactic acid film is obtained.
The preferable mass ratio of the rGO-PLA to the PLA is 1: 50. -1: 5; the organic solvent is preferably one or a mixture of two of ethanol, isopropanol, n-propanol and glycol; the vacuum heat treatment time is preferably 1 to 8 hours.
According to the invention, polylactic acid graft modified reduced graphene oxide with good compatibility with polylactic acid is prepared by forming ether bonds through simple alkaline condensation suitable for industrial production and carrying out a photo-initiated free radical reaction, and then the modified reduced graphene oxide doped polylactic acid composite phase-change film material is prepared by adopting a solution casting film forming technology commonly used in the industry, so that the modified reduced graphene oxide doped polylactic acid composite phase-change film material can be applied to a cooling filter rod section for heating non-burning cigarettes, and the smoke temperature is effectively reduced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the existing polylactic acid and polylactic acid composite material applied to the cooling filter rod section of the cigarette without burning, the phase-change auxiliary material used for reducing the graphene oxide is modified by polylactic acid grafting, has good compatibility with the main polylactic acid material, can realize the uniform distribution of the graphene in the film, forms a uniform heat-conducting network in the film and achieves better cooling effect.
2. The introduced reduced graphene oxide has higher specific surface area and oxygen-containing functional groups, can provide corresponding space for loading spices with different tastes, and is favorable for developing novel tobaccos with different tastes.
3. The adopted condensation technology, photoinitiated free radical reaction and tape casting film forming technology have simple and convenient equipment and operation process required by the technology, and are suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic diagram of a preparation process of a polylactic acid graft-modified reduced graphene oxide material used in the present invention.
FIG. 2 is a scanning electron micrograph of rGO-PLA prepared in example 1.
Fig. 3 is a scanning electron micrograph of the modified reduced graphene oxide-doped polylactic acid thin film prepared in example 1.
Fig. 4 is a graph of thermal conductivity of the film materials prepared in example 1, example 2, example 3, example 4 and a control sample of pure PLA film.
Detailed Description
The present invention will be better understood from the following examples, which are set forth to illustrate specific embodiments of the invention.
Example 1
A preparation method of a modified reduced graphene oxide doped polylactic acid film comprises the following steps:
(1) Preparing benzophenone grafted modified reduced graphene oxide: under the protection of inert gas, 0.5g of 4-hydroxy-benzophenone (BP-OH) and 5g of rGO are dispersed into 120mL of ethanol; adding 1g of potassium carbonate as a catalyst into the dispersion system, fully stirring, heating to boil, and reacting for 8 hours under a reflux condition; after the reaction is finished, the temperature of a reaction system is reduced to room temperature, rGO is centrifugally separated, the reaction system is washed with water for three times to remove potassium carbonate, and the reaction system is frozen and dried to obtain 5.16g of benzophenone grafted and modified rGO (rGO-BP).
(2) Preparing polylactic acid grafted modified reduced graphene oxide: the preparation process is shown in figure 1, 1g of PLA (with the average molecular weight of 152000 g/mol) and 4g of rGO-BP are mixed and uniformly dispersed in 100mL of ethanol; and (3) placing the dispersion under an ultraviolet lamp with the wavelength of 356nm for radiation grafting reaction for 20min, centrifugally separating rGO, washing with deionized water and ethanol for three times in sequence to remove ungrafted PLA, and freeze-drying to obtain 4.56g of PLA grafted rGO (rGO-PLA). FIG. 2 is a scanning electron micrograph of the prepared rGO-PLA from which it can be seen that grafting of PLA did not alter the lamellar morphology of the rGO.
(3) Preparing a modified reduced graphene oxide doped polylactic acid film: uniformly mixing and dispersing 2g of rGO-PLA and 10g of PLA in 50mL of isopropanol; pouring the dispersion liquid into a polytetrafluoroethylene culture dish with the diameter of 15cm, volatilizing a solvent in an oven preheated to 60 ℃ to prepare a film, and carrying out vacuum treatment on the obtained film at 80 ℃ for 2h to obtain the modified reduced graphene oxide doped polylactic acid film, wherein the average thickness of the film is 140 micrometers. FIG. 3 is a scanning electron micrograph of the prepared film, from which it can be seen that the surface of the film is relatively flat and no defects or cracks are evident. FIG. 4 is a graph showing the thermal conductivity of the film prepared in this example, 0.61W/mK; the glass transition temperature of the film was 45.4 ℃ and the melting temperature was 158 ℃ by differential scanning calorimetry.
Example 2
The experimental procedure was the same as in example 1 except that in step (3) the amount of rGO-PLA used was 1g, the vacuum heat treatment time was 8 hours, the thickness of the film produced was 126 microns, the thermal conductivity of the film was 0.52W/mK, the glass transition temperature of the film was 43.3oC, and the melting temperature was 159oC.
Example 3
The experimental procedure was the same as in example 1, except that the molecular weight of PLA in step (2) was 300000g/mol, the amount of PLA used was 0.4g, and the UV irradiation time was 1 hour; the amount of rGO-PLA used in the step (3) is 0.75g, the amount of PLA is 10.75g, the vacuum heat treatment time is 1h, the thickness of the prepared film is 130 micrometers, the thermal conductivity of the film is 0.42W/mK, the glass transition temperature of the film is 39.1 ℃ and the melting temperature is 157 ℃.
Example 4
The experimental procedure was the same as in example 1, except that the molecular weight of PLA in step (2) was 10000g/mol, the amount of PLA was 0.2g, and the UV irradiation time was 1h; the amount of rGO-PLA used in step (3) was 0.5g, the thickness of the film prepared was 123 microns, the thermal conductivity of the film was 0.28W/mK, the glass transition temperature of the film was 36.9oC, and the melting temperature was 158oC.
Example 5
The experimental procedure was the same as in example 1, except that in step (1), 0.25g of 4-hydroxybenzophenone, 0.25g of potassium carbonate, isopropanol as a solvent, a reflux time of 12 hours, a film thickness of 137 μm and a thermal conductivity of 0.60W/mK were used; the glass transition temperature of the film was 45.1 ℃ and the melting temperature was 158 ℃.
Example 6
The experimental procedure was the same as in example 1 except that the amount of 4-hydroxybenzophenone used in step (1) was 5g, the reflux time was 4 hours, the thickness of the prepared film was 133 μm, and the thermal conductivity was 0.61W/mK; the glass transition temperature of the film was 45.2 ℃ and the melting temperature was 157 ℃.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a modified reduced graphene oxide doped polylactic acid film is characterized by comprising the following steps: the preparation method of the film material, in which the doped modified reduced graphene oxide is polylactic acid grafted reduced graphene oxide, comprises the following steps:
(1) Preparing benzophenone grafted modified reduced graphene oxide: under the protection of inert gas, dispersing 4-hydroxy-benzophenone (BP-OH) and rGO in a certain proportion into an organic solvent; adding a certain amount of potassium carbonate serving as a catalyst into the dispersion system, fully stirring and heating to boil, and reacting for a certain time under a reflux condition; after the reaction is finished, cooling the temperature of a reaction system to room temperature, centrifugally separating rGO, fully washing with water to remove potassium carbonate, and freeze-drying to obtain benzophenone grafted and modified rGO, namely rGO-BP; the mass ratio of BP-OH to rGO is 1: 1. 1 to a total of: 20; the mass ratio of the potassium carbonate to the rGO is 1:5. -1: 20;
(2) Preparing polylactic acid grafted modified reduced graphene oxide: mixing PLA and rGO-BP in a certain proportion in a solvent and uniformly dispersing; placing the dispersion liquid under an ultraviolet lamp for radiation grafting reaction for a certain time, centrifugally separating rGO, fully washing by using a solvent to remove ungrafted PLA, and freeze-drying to obtain PLA grafted rGO, namely rGO-PLA; the molecular weight of the PLA is 10000-300000 g/mol; the mass ratio of the PLA to the rGO-BP is 1: 20. 1 to a total of: 1;
(3) Preparing a modified reduced graphene oxide doped polylactic acid film: uniformly mixing rGO-PLA and PLA according to a certain proportion and dispersing into an organic solvent; preparing the dispersion liquid into a film by solvent volatilization by adopting a solution casting method, and carrying out vacuum treatment on the obtained film at 80 ℃ for a certain time to obtain a modified reduced graphene oxide doped polylactic acid film; the mass ratio of the rGO-PLA to the PLA is 1: 50. 1 to a total of: 5.
2. the preparation method of the modified reduced graphene oxide-doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the organic solvent in the step (1) is one of ethanol, normal propyl alcohol, isopropanol, ethylene glycol, acetonitrile, tetrahydrofuran and dioxane.
3. The preparation method of the modified reduced graphene oxide-doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the reflux reaction time in the step (1) is 4 to 12 hours.
4. The preparation method of the modified reduced graphene oxide-doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the solvent in the step (2) is water or an alcohol organic solvent capable of dissolving PLA.
5. The preparation method of the modified reduced graphene oxide doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the radiation grafting reaction time in the step (2) is 5 to 60 minutes.
6. The preparation method of the modified reduced graphene oxide doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the wavelength of the ultraviolet light in the step (2) is 365 nanometers.
7. The preparation method of the modified reduced graphene oxide-doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the organic solvent is one or a mixture of two of ethanol, isopropanol, n-propanol and glycol.
8. The preparation method of the modified reduced graphene oxide-doped polylactic acid film according to claim 1, wherein the preparation method comprises the following steps: the vacuum heat treatment time in the step (3) is 1 to 8 hours.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203184A (en) * | 2008-11-05 | 2011-09-28 | 帝人化成株式会社 | Polylactic acid compositions and molded articles thereof |
| CN103086367A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of polylactic acid functionalized graphene |
| CN104937009A (en) * | 2012-12-20 | 2015-09-23 | 沙特基础全球技术有限公司 | Blends containing photoactive additives |
| CN107216462A (en) * | 2017-06-09 | 2017-09-29 | 大连大学 | A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition |
| CN107227005A (en) * | 2016-03-24 | 2017-10-03 | 东南大学 | A kind of preparation method of modified graphene oxide/lactic acid composite material |
| CN108912626A (en) * | 2018-04-11 | 2018-11-30 | 西安理工大学 | Functional graphene oxide/lactic acid composite material air blocking thin film preparation method |
| CN109627685A (en) * | 2018-10-29 | 2019-04-16 | 徐冬 | A kind of UV barrier film |
| AU2019206096A1 (en) * | 2018-08-13 | 2020-02-27 | Shaanxi University Of Technology | Polylactic acid film modified by organic-inorganic hybrid particles and method for producing same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2935396A1 (en) * | 2012-12-20 | 2015-10-28 | SABIC Global Technologies B.V. | Cross-linked polycarbonate resin with improved chemical and flame resistance |
| EP3626758B1 (en) * | 2017-06-26 | 2022-04-06 | Hangzhou Gaoxi Technology Co., Ltd. | Graphene composite material and preparation method therefor |
-
2020
- 2020-08-20 CN CN202010839969.3A patent/CN112094421B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203184A (en) * | 2008-11-05 | 2011-09-28 | 帝人化成株式会社 | Polylactic acid compositions and molded articles thereof |
| CN104937009A (en) * | 2012-12-20 | 2015-09-23 | 沙特基础全球技术有限公司 | Blends containing photoactive additives |
| CN103086367A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of polylactic acid functionalized graphene |
| CN107227005A (en) * | 2016-03-24 | 2017-10-03 | 东南大学 | A kind of preparation method of modified graphene oxide/lactic acid composite material |
| CN107216462A (en) * | 2017-06-09 | 2017-09-29 | 大连大学 | A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition |
| CN108912626A (en) * | 2018-04-11 | 2018-11-30 | 西安理工大学 | Functional graphene oxide/lactic acid composite material air blocking thin film preparation method |
| AU2019206096A1 (en) * | 2018-08-13 | 2020-02-27 | Shaanxi University Of Technology | Polylactic acid film modified by organic-inorganic hybrid particles and method for producing same |
| CN109627685A (en) * | 2018-10-29 | 2019-04-16 | 徐冬 | A kind of UV barrier film |
Non-Patent Citations (2)
| Title |
|---|
| Improvement of viscoelastic, elastic and plastic properties of Poly(L-lactide)/Graphene Oxide-Graft-Poly(L-lactide) nanocomposites by modulation of grafted chain length;Campos, JM et al.;《COMPOSITES SCIENCE AND TECHNOLOGY》;20200710;第199卷;文献号108350 * |
| 表面接枝二苯甲酮光活性聚合物及光化学;康慧等;《北京化工大学学报(自然科学版)》;20110531;第38卷(第5期);第75-80页 * |
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