CN115490889A - Method for realizing in-situ stripping of two-dimensional filler by using high-elasticity polymer - Google Patents
Method for realizing in-situ stripping of two-dimensional filler by using high-elasticity polymer Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
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- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention relates to the technical field of nano-fillers, and discloses a method for realizing in-situ stripping of a two-dimensional filler by using a high-elasticity polymer, which comprises the following steps: step one, heating a polymer through equipment to enable the polymer to be in a high-elasticity state; secondly, providing strong stress for the polymer in the high elastic state through processing equipment, wherein the polymer in the high elastic state is forced to flow, and molecular chains of the polymer forced to flow are subjected to irreversible molecular motion to generate strong shearing stress; directly mixing the two-dimensional filler powder which is not peeled into the flowing high-elasticity polymer, so that the strong shearing stress in the flowing high-elasticity polymer matrix can act on the two-dimensional filler; and step four, after the mixed sample is subjected to forced flow processing for a certain time, all the two-dimensional fillers are sheared and stripped by fully saturated strong shearing stress, and finally the dispersed two-dimensional nano material successfully stripped in situ is obtained. The method is simple, efficient, green and environment-friendly, and the two-dimensional filler is stripped by a solvent-free method.
Description
Technical Field
The invention relates to the technical field of nano-fillers, in particular to a method for realizing in-situ stripping of a two-dimensional filler by using a high-elasticity polymer.
Background
With the continuous development of polymer composites, the morphology and size of the filler also play a very important role as an important structural parameter. The two-dimensional nano material has anisotropy, and the directions of a vertical plane and a parallel plane of the two-dimensional nano material have different physical and chemical properties. Therefore, the in-plane size and thickness of the two-dimensional nano material can directly influence the mechanical, heat-resistant, electric-conductive, heat-conductive, blocking, electromagnetic shielding and other properties and functions of the polymer-based composite material. The preparation of the two-dimensional nano material with lower thickness is the main direction of high-performance and multifunctional modification of the composite material. The stripping of the existing two-dimensional filler can obviously reduce the thickness of the filler and exert the characteristics of the two-dimensional filler in the composite material. Typically, graphite is exfoliated into graphite nanosheets or graphene, and the exfoliated graphite exfoliates to enable the composite material to have more excellent characteristics.
The existing stripping method needs to use a large amount of solvent, has complicated steps, and has different requirements on different two-dimensional fillers, such as specific dispersing solvent, specific dispersing equipment method, post-treatment conditions and the like; the existing method has low yield, high cost and strict requirements on conditions; some methods have high energy consumption, long period, large damage to the transverse size of the two-dimensional filler and the like. In addition, there is a natural disadvantage in the case of polymer composites, that is, the need for redispersion in the polymer matrix, the size of the exfoliation of which does not represent the final size in the composite (which is directly influenced by the dispersing effect). This limits the two-dimensional filler from exerting its dimensional effect in the polymer composite. Therefore, the method for stripping the two-dimensional filler, which is simple, efficient, green and environment-friendly and has no solvent, is very important for the development of the composite material.
Disclosure of Invention
The invention aims to provide a method for realizing in-situ stripping of a two-dimensional filler by using a high-elasticity polymer, and aims to solve the problems that the existing stripping method needs a large amount of solvents and is complicated in steps, the requirements for different two-dimensional nano fillers are different, the existing method is low in yield and high in cost, the requirements for conditions are strict or the energy consumption is high, the period is long, and the damage to the transverse dimension of the two-dimensional filler is large.
In order to achieve the above purpose, the basic scheme of the invention is as follows: a method for realizing in-situ peeling of a two-dimensional filler by using a high-elasticity polymer comprises the following steps:
step one, heating a polymer through equipment to enable the polymer to be in a high elastic state;
secondly, providing strong stress for the polymer in the high elastic state through processing equipment, wherein the polymer in the high elastic state is forced to flow, and molecular chains of the polymer forced to flow are subjected to irreversible molecular motion to generate strong shearing stress;
directly mixing the two-dimensional filler powder which is not peeled into the flowing high-elasticity polymer, so that the strong shearing stress in the flowing high-elasticity polymer matrix can act on the two-dimensional filler;
and step four, after the mixed sample is subjected to forced flow processing for a certain time, all the two-dimensional fillers are sheared and stripped by fully saturated strong shearing stress, and finally the dispersed two-dimensional nano material successfully stripped in situ is obtained.
Principle of the basic scheme: the method utilizes the extremely high viscosity of the high elastic polymer to generate extremely large stress when the high elastic polymer flows under the action of external force, and can effectively lead the two-dimensional filler dispersed in the high elastic polymer to generate destructive deformation so as to lead the two-dimensional filler to start to be destroyed from weak layers. The polymer in the high elastic state has special molecular chain motion behavior, and when the polymer flows without external force, the molecular chain does not have free thermal motion. This results in that each forced flow of the polymer in the high elastic state effectively exerts a force on the two-dimensional filler, and the molecular chains automatically fill the peeling position without causing the two-dimensional filler peeled by the external force to be recombined due to the thermal movement of the molecules. The characteristics of the high elastic state polymer enable the two-dimensional filler to be continuously stripped, and finally the two-dimensional nano material is obtained.
The basic scheme has the advantages that: the problems that the existing stripping method needs to use a large amount of solvents and has complex steps, the requirements for different two-dimensional nano fillers are different, the existing stripping method is low in yield, high in cost, harsh in requirements for conditions or high in energy consumption, long in period and large in damage to the transverse size of the two-dimensional nano filler are solved.
Further, the specific process of the step one is as follows: the polymer is heated to a temperature between the glass transition temperature and the viscous flow temperature through the equipment, so that the polymer becomes amorphous polymer between the glass transition temperature and the viscous flow temperature, and the chain segment of the polymer is in a movable state without thermal movement of the molecular chain.
Principle of the basic scheme: the polymer is brought to a high elastic state by the apparatus by raising the temperature of the polymer to between the glass transition temperature and the viscous flow temperature.
Further, the specific process of the second step is as follows: the polymer in high elastic state is provided with strong stress through melt processing equipment, so that the polymer in high elastic state generates forced flow, and the flowing polymer in high elastic state generates strong shear stress through mechanical equipment.
Further, the fourth specific process of the step is as follows: and (3) packing and milling the blend in the first step, the second step and the third step for a single time or multiple times to obtain the monodisperse two-dimensional nano filler master batch in the high-elasticity polymer medium.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method does not need to use a large amount of solvent, has simple steps, and can be suitable for different two-dimensional nano fillers, such as the like; the method has high yield, low cost and no strict requirements on conditions; and the damage to the transverse dimension of the two-dimensional nano filler is small.
(2) The high elastic state polymer has extremely high viscosity, and generates extremely large stress when the high elastic state polymer flows under the action of external force, so that the two-dimensional nano filler dispersed in the high elastic state polymer can be effectively damaged and deformed, and the two-dimensional filler starts to be damaged from weak layers. The polymer in the high elastic state has special molecular chain motion behavior, and when the polymer flows without external force, the molecular chain does not have free thermal motion. This results in that the polymer in a high elastic state can effectively apply a force to the two-dimensional nanofiller each time forced flow occurs, and the molecular chains automatically fill the peeling position without re-binding the two-dimensional nanofillers peeled by an external force due to the thermal movement of the molecules. The nature of these high elastic state polymers allows for constant exfoliation of the two-dimensional nanofiller.
(3) The environment is protected, and toxic and harmful products are not used and generated; the method is efficient and energy-saving, and can strip the two-dimensional filler in a large scale in a short time; in-situ stripping, wherein the stripped two-dimensional filler is monodisperse in a polymer matrix and can be directly used or used as master batch; the method has wide applicability, is effective to various polymers with high elasticity, and has certain stripping effect on various two-dimensional fillers.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a flow chart of a method for achieving in situ exfoliation of a two-dimensional filler using a high-elasticity polymer according to an embodiment of the present invention;
FIG. 2 is a SEM image of a graphite powder used in experiment one of the present invention;
FIG. 3 is a SEM image of in-situ dispersion of graphite after exfoliation in a first experiment of the present invention;
FIG. 4 is a SEM image of a boron nitride powder used in experiment two of the present invention;
FIG. 5 is a SEM image of a post-strip and in-situ dispersion of boron nitride in experiment two of the present invention;
FIG. 6 is a SEM image of graphite exfoliated and dispersed at high content in experiment three of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The following is further detailed by way of specific embodiments:
the embodiment is substantially as shown in figures 1 and 2: a method for realizing in-situ peeling of a two-dimensional filler by using a high-elasticity polymer comprises the following steps:
step one, heating a polymer through equipment to enable the polymer to be in a high-elasticity state;
secondly, providing strong stress for the polymer in the high elastic state through processing equipment, wherein the polymer in the high elastic state is forced to flow, and molecular chains of the polymer forced to flow are subjected to irreversible molecular motion to generate strong shearing stress;
directly mixing the two-dimensional filler powder which is not peeled into the flowing high-elasticity polymer, so that the strong shearing stress in the flowing high-elasticity polymer matrix can act on the two-dimensional filler;
and step four, after the mixed sample is subjected to forced flow processing for a certain time, all the two-dimensional fillers are sheared and peeled by fully saturated strong shearing stress, and finally the dispersed in-situ peeled successful two-dimensional nano material is obtained.
The specific implementation process is as follows: the method utilizes the extremely high viscosity of the high elastic polymer to generate extremely large stress when the high elastic polymer flows under the action of external force, and can effectively lead the two-dimensional filler dispersed in the high elastic polymer to generate destructive deformation so as to lead the two-dimensional filler to start to be destroyed from weak layers. The polymer in the high elastic state has special molecular chain motion behavior, and when the polymer flows without external force, the molecular chain does not have free thermal motion. This results in that each forced flow of the polymer in the high elastic state effectively exerts a force on the two-dimensional filler, and the molecular chains automatically fill the peeling position without causing the two-dimensional filler peeled by the external force to be recombined due to the thermal movement of the molecules. The characteristics of the high elastic state polymer enable the two-dimensional filler to be continuously stripped, and finally the two-dimensional nano material is obtained.
The specific process of the step one is as follows: the polymer is heated to a temperature between the glass transition temperature and the viscous flow temperature through the equipment, so that the polymer becomes amorphous polymer between the glass transition temperature and the viscous flow temperature, and the chain segment of the polymer is in a movable state without thermal movement of the molecular chain.
The specific implementation process is as follows: the polymer is brought to a high elastic state by the apparatus by raising the temperature of the polymer to between the glass transition temperature and the viscous flow temperature.
The specific process of the second step is as follows: the polymer in high elastic state is provided with strong stress through melt processing equipment, the polymer in high elastic state is forced to flow, and the flowing polymer in high elastic state generates strong shear stress through mechanical equipment.
The fourth specific process is as follows: and (3) packing and milling the blend in the first step, the second step and the third step for a single time or multiple times to obtain the monodisperse two-dimensional nano filler master batch in the high-elasticity polymer medium.
In order to prove the creativity and the technical value of the technical scheme of the invention, the part is to carry out experiments and comparative experiments on specific products or related technologies on the technical scheme of the claims.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Experiment one:
a method for realizing in-situ peeling of a two-dimensional filler by using a high-elasticity polymer is realized by the following scheme:
(1) 4060D 59.5g of polylactic acid (NatureWorks) and 6.5g of graphite are weighed, and the polylactic acid and the graphite are dried in a vacuum oven at 50 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 90 ℃ with a front roll speed of 10rpm, a rear roll speed of 8rpm and a front and rear roll gap of 0.15mm.
(3) The dried polylactic acid was fed into a two roll mill and dried graphite was added as the polylactic acid flowed between the rolls.
(4) Taking out the sample sheet of the wrapping roller, performing triangular wrapping, feeding again, and repeating for 7-8 times.
(5) And finally taking out the sheet sample for the first time, and cooling the sheet sample to room temperature.
As shown in fig. 2 and 3, illustrating that the graphite achieves in-situ exfoliation and in-situ dispersion.
Experiment two:
(1) The polylactic acid 4060D 52g (NatureWorks corporation) and the boron nitride 13g were weighed and dried in a vacuum oven at 50 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 90 ℃ with a front roll speed of 10rpm, a rear roll speed of 8rpm and a front and rear roll gap of 0.15mm.
(3) The dried polylactic acid was fed into a two roll mill and dried boron nitride was added as the polylactic acid flowed between the rolls.
(4) Taking out the sample sheet of the wrapping roller, performing triangular wrapping, feeding again, and repeating for 7-8 times.
(5) And finally taking out the flaky sample for the last time, and cooling the flaky sample to room temperature.
As shown in fig. 4 and 5, experiment two differs from experiment one in that the two-dimensional filler used was changed from graphite to hexagonal boron nitride, which still achieved exfoliation and in-situ dispersion.
Experiment three:
(1) Weighing 4060D 40g (NatureWorks corporation) of polylactic acid and 40g of graphite, and drying the polylactic acid and the graphite in a vacuum oven at 50 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 90 ℃ with a front roll speed of 10rpm and a rear roll speed of 8rpm, at a roll gap of 0.15mm.
(3) The dried polylactic acid was fed into a two roll mill and dried graphite was added as the polylactic acid flowed between the rolls.
(4) Taking out the sample sheet of the wrapping roller, performing triangular wrapping, feeding again, and repeating for 7-8 times.
(5) And finally taking out the sheet sample for the first time, and cooling the sheet sample to room temperature.
Experiment three differed from experiment one in that the graphite content increased from 10wt% to 50wt%, as shown in fig. 6, and the graphite was exfoliated and dispersed in situ in the polymer matrix at the high content, as shown in fig. 6.
Experiment four:
(1) 65g of polycarbonate PC and 43g of graphite are weighed and dried in a vacuum oven at 120 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 170 ℃ with a front roll speed of 10rpm, a rear roll speed of 8rpm and a front and rear roll gap of 0.15mm.
(3) The dried polycarbonate was fed into a two roll mill and dried graphite was added as the polycarbonate flowed between the rolls.
(4) Taking out the roller sample sheet, performing triangular bag packaging, feeding again, and repeating for 7-8 times.
(5) And finally taking out the sheet sample for the first time, and cooling the sheet sample to room temperature.
Experiment five:
(1) 65g of polymethyl methacrylate PMMA (NatureWorks company) and 43g of graphite were weighed, and the polymethyl methacrylate and the carbon nanotubes were dried in a vacuum oven at 120 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 150 ℃ with a front roll speed of 10rpm, a rear roll speed of 8rpm and a front-to-rear roll gap of 0.15mm.
(3) The dried polymethylmethacrylate is fed into a two roll mill and the dried graphite is added as the polymethylmethacrylate flows between the rolls.
(4) Taking out the sample sheet of the wrapping roller, performing triangular wrapping, feeding again, and repeating for 7-8 times.
(5) And finally taking out the sheet sample for the first time, and cooling the sheet sample to room temperature.
Experiment six:
(1) Weighing 4060D 40g (NatureWorks corporation) of polylactic acid and 40g of montmorillonite, and drying the polylactic acid and montmorillonite in a vacuum oven at 50 ℃ for 5 hours.
(2) A two-roll mill was used at a temperature of 90 ℃ with a front roll speed of 10rpm and a rear roll speed of 8rpm, at a roll gap of 0.15mm.
(3) Feeding the dried polylactic acid into a two-roll mill, and adding the dried montmorillonite when the polylactic acid flows between the rolls
(4) Taking out the sample sheet of the wrapping roller, performing triangular wrapping, feeding again, and repeating for 7-8 times.
(5) And finally taking out the sheet sample for the first time, and cooling the sheet sample to room temperature.
Some positive effects achieved in the process of research and development or use of the invention are indeed great advantages compared to the prior art, and the following description is made in combination with data, diagrams and the like of experimental processes.
And in the fourth experiment and the fifth experiment, the higher glass transition material is adopted as a dispersing matrix, and the graphite is stripped and dispersed in situ.
Experiment six is a contribution of the present invention to the dispersion of other two-dimensional fillers.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and/or features of the schemes is not described herein in excess. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (4)
1. A method for realizing in-situ peeling of a two-dimensional filler by using a high-elasticity polymer is characterized by comprising the following steps: the method comprises the following steps:
step one, heating a polymer through equipment to enable the polymer to be in a high elastic state;
secondly, providing strong stress for the polymer in the high elastic state through processing equipment, wherein the polymer in the high elastic state is forced to flow, and molecular chains of the polymer forced to flow are subjected to irreversible molecular motion to generate strong shearing stress;
directly mixing the two-dimensional filler powder which is not peeled into the flowing high-elasticity polymer, so that the strong shearing stress in the flowing high-elasticity polymer matrix can act on the two-dimensional filler;
and step four, after the mixed sample is subjected to forced flow processing for a certain time, all the two-dimensional fillers are sheared and peeled by fully saturated strong shearing stress, and finally the dispersed in-situ peeled successful two-dimensional nano material is obtained.
2. The method for realizing in-situ exfoliation of two-dimensional fillers with high elastomeric polymers as claimed in claim 1, wherein: the specific process of the first step is as follows: the polymer is heated to a temperature between the glass transition temperature and the viscous flow temperature by the device, so that the polymer is in a high-elastic state, and the chain segment of the polymer is in a movable state without thermal movement of the molecular chain.
3. The method for realizing in-situ exfoliation of two-dimensional fillers with high elastomeric polymers as claimed in claim 1, wherein: the specific process of the second step is as follows: the polymer in high elastic state is provided with strong stress through melt processing equipment, the polymer in high elastic state is forced to flow, and the flowing polymer in high elastic state generates strong shear stress through mechanical equipment.
4. The method for realizing in-situ exfoliation of two-dimensional fillers with high elastomeric polymers as claimed in claim 1, wherein: the fourth specific process of the step is as follows: and (3) packing and milling the blend in the first step, the second step and the third step for a plurality of times to obtain the two-dimensional nano filler master batch which is peeled off in situ and uniformly dispersed in the high-elasticity polymer medium.
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