CN113717506B - Graphene-degradable resin master batch and preparation method and application thereof - Google Patents
Graphene-degradable resin master batch and preparation method and application thereof Download PDFInfo
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- CN113717506B CN113717506B CN202111159496.3A CN202111159496A CN113717506B CN 113717506 B CN113717506 B CN 113717506B CN 202111159496 A CN202111159496 A CN 202111159496A CN 113717506 B CN113717506 B CN 113717506B
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- 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
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- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention relates to the field of degradable membrane materials. More specifically, the invention relates to a preparation method and application of a graphene-degradable resin master batch. A preparation method of graphene-degradable plastic resin master batch comprises the following steps: s1, preparing two parts of N, N-dimethylformamide solution, respectively ultrasonically dispersing graphene and a chain extender in the N, N-dimethylformamide solution, adding the N, N-dimethylformamide solution containing the graphene into the N, N-dimethylformamide solution containing the chain extender under the stirring condition, uniformly stirring, carrying out suction filtration and freeze drying to obtain modified graphene; specifically, 1-10 g of graphene is dispersed in a 1L N, N dimethylformamide solution, and 10-100 g of a chain extender is dissolved in the 1L N, N dimethylformamide solution; and S2, mixing and stirring the modified graphene, the antioxidant and the degradable resin particles, and then sequentially carrying out melting, extrusion, water cooling and granulation.
Description
Technical Field
The invention relates to the field of degradable membrane materials. More specifically, the invention relates to a preparation method and application of a graphene-degradable resin master batch.
Background
Graphene is a two-dimensional nanomaterial formed by hexagonal assembly of carbon atoms, is a nanomaterial which is prepared and used most at present, has a plurality of excellent properties, and is widely applied to the field of composite materials at present. The characteristics of high strength, high electrical conductivity and high thermal conductivity are mainly applied in the field of composite materials, and particularly, the mechanical property of the composite material is improved by only needing a small amount of additive.
The film material which is most used in agriculture is prepared from low-density polyethylene, and the polyethylene film material is soft in material, high in transparency and low in production cost, can keep soil humidity, improve soil temperature and prevent pests and microorganisms from damaging plants, and is applied to crops such as peanuts, corns, tobaccos and various vegetables. The black film material is obtained by doping carbon black in the resin master batch, and compared with a white film material, the black film material has the following advantages: the fertilizer retention capacity is stronger, the temperature change in the film material is smaller, the temperature is 1-3 ℃ lower than that in the white film material, the fertilizer retention capacity is suitable for crops with lower soil temperature, the water retention capacity is improved by 4-10% compared with that of the white film material, in addition, sunlight is difficult to penetrate through the black film material, the sunlight absorption of weeds in the film material is hindered, and the weed growth can be inhibited. Black film materials also have disadvantages, most importantly, the rate of temperature rise within the film material is slow and the temperature is low.
Since the 70 s in the world, the usage of polyethylene film materials in China is increased year by year, and at present, the polyethylene film materials exceed 50 million tons per year, and the coverage area exceeds 2 hundred million acres, so that the polyethylene film materials become indispensable agricultural materials at present, but bring great economic effects and a plurality of environmental problems. Polyethylene is very stable under natural conditions, and is very difficult to degrade by light and microorganisms, the polyethylene can be generally treated by burning, the greenhouse effect is intensified by the method, the second national pollution source general investigation shows that the accumulated residual quantity of film materials in the soil of the mulching farmland in China reaches 118.48 ten thousand tons, the film materials can be remained in the soil for 200-400 years, and the method has great influence on the secondary cultivation of the land. Polyethylene film material can completely cut off moisture and lose, remaining membrane material can hinder during the rainwater infiltrates into the soil simultaneously, reduce the moisture permeability of soil, cause the influence to the fertility of soil and the activity of microorganism wherein, the remaining membrane material also can hinder the development of newborn seedling, make the availability factor of fertilizer and soil reduce, cause crops output to descend, remaining membrane material also can be in the same place with the fodder mixing of livestock, influence the digestive system of livestock, can make its death when serious, and further influence human health through the food chain, membrane material recovery does not thoroughly also can hinder the use of agricultural implement in addition. The following three main solutions to the above or problems exist: firstly, the device for recovering residual film materials is developed, and drum type, spring tooth type, toothed chain type, roller winding type, pneumatic type and other residual film recovery machines are available at present; secondly, a saving-type membrane material is used, the membrane material has high toughness and strong anti-aging capability and can be reused, so that the usage amount of the membrane material is reduced, but the membrane material still needs to be recovered after being used for a plurality of times; and thirdly, the degradable membrane material is developed, the degradation time can be greatly shortened by using biodegradable plastics, the formula of the membrane material can be adjusted according to the local climatic conditions such as microbial types, humidity and illumination, the requirements of crops and the like, the most suitable degradable membrane material for the local conditions is manufactured, the membrane material does not need to be recycled after being used, the soil is basically free of pollution, and the manpower and material resources are reduced. At present, the main degradable plastics are poly (butylene adipate terephthalate) (PBAT), poly (butylene succinate) (PBS), polyhydroxyalkanoate (PHA) and Polycaprolactone (PCL).
The degradable graphene membrane material has the advantages that due to the existence of degradable plastics, the degradable membrane material greatly improves the degradation speed compared with a PE (polyethylene) membrane, protects the soil environment, strongly absorbs ultraviolet rays, reduces the temperature change in the membrane material, improves the heating speed, promotes the temperature in the membrane material, can kill weeds at high temperature, and further reduces the growth rate of the weeds. The special two-dimensional material structure of the graphene enables the water molecule permeation route to be prolonged, the moisture permeability to be smaller, the moisture retention capacity to be stronger, and the humidity in the membrane material to be improved. Compared with carbon black, the graphene composite material has the advantages of smaller addition amount of graphene, higher strength of a film material and larger blackness. The invention of China with the patent number of CN 106189143A claims a polycaprolactone macromolecule degradation material and a preparation method thereof, N-dimethylacetamide solvent is adopted to disperse reinforcing phase nano particles and polycaprolactone respectively under stirring, then reinforcing phase nano magnesium oxide particles are mixed with polycaprolactone dispersion solution, the solvent is evaporated after high-temperature stirring, the master batch nano particles prepared by the method are uniformly dispersed, the crystallinity of polycaprolactone is damaged, the degradation speed is enhanced, the nano magnesium oxide has wide sources and low price, and has good high-temperature resistance stability, the toughening is enhanced and the high-temperature resistance stability of the material is improved when the nano magnesium oxide is added into a polymer, but the organic solvent is removed by an evaporation method, so that the environment is polluted and great energy is consumed; the invention discloses a degradable membrane material for planting plateau vegetables in Chinese patent with patent number CN 110117413A and a preparation method and application thereof.
Disclosure of Invention
The invention relates to preparation of a graphene-degradable plastic resin master batch.
The invention provides a preparation method of graphene-degradable plastic resin master batch, which comprises the following steps:
s1, preparing two parts of N, N-dimethylformamide solution, respectively ultrasonically dispersing graphene and a chain extender in the N, N-dimethylformamide solution, adding the N, N-dimethylformamide solution containing the graphene into the N, N-dimethylformamide solution containing the chain extender under the stirring condition, uniformly stirring, carrying out suction filtration and freeze drying to obtain modified graphene; specifically, 1-10 g of graphene is dispersed in a 1L N, N dimethylformamide solution, and 10-100 g of a chain extender is dissolved in the 1L N, N dimethylformamide solution;
s2, mixing and stirring the modified graphene, the antioxidant and the degradable resin particles, and then sequentially carrying out melting, extrusion, water cooling and granulation treatment to obtain the graphene-degradable resin master batch;
wherein the mass ratio of the graphene to the chain extender is 1:5-1, the mass fraction of the modified graphene is 0.5-5 wt% of the degradable resin particles, and the mass fraction of the antioxidant is 0.5-2 wt% of the degradable resin particles.
Preferably, the degradable resin particles are one or more of polybutylene adipate/terephthalate, polybutylene succinate, polyhydroxyalkanoate and polycaprolactone.
Preferably, the chain extender is one or more of epoxy styrene/acrylate oligomer and styrene-acrylonitrile-glycidyl methacrylate.
Preferably, the antioxidant is one or more of 1010, 1076, 1024, 1098, 245, 168, 264, 330, 990 and 405.
Preferably, the mixing time condition of the modified graphene, the antioxidant and the degradable resin particles is 1 to 3min.
Preferably, the melting temperature condition in S2 is 150 ℃ to 230 ℃.
The graphene-degradable resin master batch is prepared by the preparation method of the graphene-degradable resin master batch.
Application of the graphene-degradable resin master batch in preparing a degradable film material.
The invention at least comprises the following beneficial effects:
(1) Preparing graphene-degradable plastic master batches by two steps of solution compounding and melt compounding of graphene and degradable resin particles; the chain extender contains epoxy and amino functional groups, the graphene contains epoxy and carboxyl, the graphene can react with the chain extender at high temperature to form modified graphene, the chain extender and the graphene are compounded to realize uniform dispersion of the graphene in the master batch, the agglomeration of the graphene is reduced, the mechanical property of the material is improved, DMF (dimethyl formamide) used in the preparation process is easy to recover, and the environmental influence is small;
(2) The compatibility of the graphene and the degradable membrane material plastic is improved due to the modification of the graphene, so that the mechanical property of the degradable membrane material is improved, the water permeability of the degradable membrane material can be reduced by the graphene, the water content in soil is improved, the requirement of industrial large-scale production is met by fusion compounding, and the energy consumption and the production cost are reduced;
(3) The chain extender can improve the molecular weight of the degradable film material plastic, improve the strength of a melt, enhance the hydrolysis stability of the film material, and reduce the water permeability of the degradable film material plastic molecular chain due to crosslinking, thereby being beneficial to improving the film blowing production rate and the material mechanical property.
(4) The mechanical strength and the elongation at break of the degradable membrane material are obviously improved by adding the graphene, and the degradable performance of the PBAT is not influenced;
(5) The degradable film material prepared by the graphene-degradable resin master batch is adopted, the chain extender is used as a bridge to connect the graphene and the degradable resin particles, the compatibility of the self-assembled graphene and the degradable resin particles is improved through the self-assembly of the chain extender on the surface of the graphene and the interaction between the graphene and the degradable resin groups, and the interface between the graphene and the degradable resin particle matrix is tighter; in addition, the chain extender is self-assembled on the surface of the graphene, so that the interlayer spacing of the graphene is increased, degradable resin molecules are easily intercalated between graphene sheets in a molten composite state, the reaction between the self-assembled graphene and the degradable resin groups is realized, the agglomeration of the graphene in the degradable resin particle matrix is reduced, the enhancement effect of the graphene is maximized, and the improvement of the toughness and the strength of the membrane material is realized. In addition, the process combines two methods of solution compounding and melt compounding, namely the solution compounding is used for realizing the uniform dispersion of the graphene, the melt compounding is also used for meeting the requirements of industrial production, the production cost is reduced, and the large-scale production can be realized.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
A preparation method of graphene-degradable resin master batch comprises the following steps:
s1, preparing two parts of N, N dimethylformamide solutions, respectively ultrasonically dispersing graphene and a chain extender in the N, N dimethylformamide solutions, adding the N, N dimethylformamide solution containing the graphene into the N, N dimethylformamide solution containing the chain extender under the condition of stirring, and performing suction filtration and freeze drying after uniformly stirring to obtain modified graphene; specifically, 1-10 g of graphene is dispersed in a 1L N, N dimethylformamide solution, and 10-100 g of a chain extender is dissolved in the 1L N, N dimethylformamide solution.
And S2, mixing and stirring the graphene assembled and modified by the chain extender, the antioxidant and the degradable resin Particles (PBAT) for 1-3 min, adding the mixture into a double screw to perform melt mixing at the temperature of 150-230 ℃, and performing extrusion, water cooling and granulation treatment to obtain the graphene-degradable resin master batch.
The mass ratio of the graphene to the chain extender is 1:5-1, the mass fraction of the graphene assembled and modified by the chain extender is 0.5-5 wt% of the degradable resin particles, and the mass fraction of the antioxidant is 0.5-2 wt% of the degradable resin particles.
Specifically, the degradable resin particles are one or a mixture of more of polybutylene adipate/terephthalate, polybutylene succinate, polyhydroxyalkanoate and polycaprolactone.
Specifically, the chain extender is one or more of epoxy styrene/acrylate oligomer (ADR-4468, ADP-1200, ADR-4370, ADR-4400, ADR-4368 and ADR-4300), styrene-acrylonitrile-glycidyl methacrylate (SAG-001, SAG-002, SAG-005 and SAG-008).
Specifically, the antioxidant is one or more of 1010, 1076, 1024, 1098, 245, 168, 264, 330, 990 and 405.
< example 1>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps:
s1, preparing 200ml of DMF, respectively ultrasonically dispersing 1g of graphene and 10g of SAG-008 in DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008 under stirring, uniformly stirring, filtering, recovering the DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene is 0.5wt% of the PBAT.
And adding the master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the graphene-PBAT degradable mulching film material.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amide bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 2>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
S1, respectively preparing 200ml and 100ml of DMF, respectively ultrasonically dispersing 1g of graphene and 5g of ADR-4370 in 200ml and 100ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing ADR-4370 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the fact that hydroxyl and carboxyl exist on the surface of the graphene, ADR-4370 is adsorbed on the surface of the graphene through a hydrogen bond effect to achieve modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene is 0.5wt% of the PBAT.
And adding the master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the graphene-PBAT degradable mulching film material.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 3>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
S1, respectively preparing 200ml and 100ml of DMF, respectively ultrasonically dispersing 1g of graphene and 5g of SAG-008 in 200ml and 100ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene is 0.5wt% of the PBAT.
And adding the master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the graphene-PBAT degradable mulching film material.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 4>
The embodiment relates to a preparation method of graphene-degradable resin master batches and a method for blow molding of the graphene-degradable resin master batches into a film material, and the method specifically comprises the following steps:
s1, preparing 200mlDMF, ultrasonically dispersing 1g of graphene and 10g of SAG-008 in DMF respectively, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the fact that hydroxyl and carboxyl exist on the surface of the graphene, SAG-008 adsorbs on the surface of the graphene through a hydrogen bond effect to achieve modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PE into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 190-220 ℃, the rotating speed is 15r/min, and the graphene is 0.5wt% of the PE.
And adding the master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the graphene-PE mulching film material.
< example 5>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
S1, respectively preparing 200ml and 100ml of DMF, respectively ultrasonically dispersing 1g of graphene and 7g of SAG-008 in 200ml and 100ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, ADR-4370 is adsorbed on the surface of the graphene through the action of hydrogen bonds to realize the modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 0.5wt% of the PBAT.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 6>
The embodiment relates to a preparation method of a graphene-degradable resin master batch, which specifically comprises the following steps:
s1, preparing 100mlDMF, respectively ultrasonically dispersing 0.1g of graphene and 1g of SAG-008 in 100ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing SAG-008 while stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the modification of the graphene.
S2, adding 20g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 1min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene is 2wt% of the PBAT.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 7>
The embodiment relates to a preparation method of a graphene-degradable resin master batch, which specifically comprises the following steps:
s1, preparing 100mlDMF, ultrasonically dispersing 1g of graphene and 10g of SAG-008 in 100ml of DMF respectively, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the modification of the graphene.
S2, adding 50g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 5wt% of the PBAT.
Epoxy groups and amino groups exist on the surface of the graphene assembled and modified by the chain extender, and the graphene and the ester groups in the PBAT react at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the graphene assembled and modified by the chain extender can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 8>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
S1, respectively preparing 200ml of DMF and 100mlDMF, respectively ultrasonically dispersing 1g of graphene and 10g of SAG-008 in 200ml of DMF and 100mlDMF, slowly adding the DMF solution containing the graphene into the DMF solution containing SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the fact that hydroxyl and carboxyl exist on the surface of the graphene, SAG-008 adsorbs on the surface of the graphene through a hydrogen bond effect to achieve modification of the graphene.
S2, adding 5g of modified graphene, 10g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 0.5wt% of the PBAT.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 9>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
S1, respectively preparing 200ml of DMF and 100mlDMF, respectively ultrasonically dispersing 1g of graphene and 10g of SAG-008 in 200ml of DMF and 100mlDMF, slowly adding the DMF solution containing the graphene into the DMF solution containing SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the modification of the graphene.
S2, adding 5g of modified graphene, 20g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 0.5wt% of PBS.
Epoxy groups and amino groups on the surface of the modified graphene react with ester groups in the PBAT at a high temperature in the twin-screw to generate amide bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, the original hydrogen bonds on the surface of the modified graphene can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< example 10>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
Respectively ultrasonically dispersing S1, 1g of graphene and 10g of SAG-008 in 200ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the assembly modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1024 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw, and performing melt water-cooling granulation to obtain black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 0.5wt% of the PBAT.
Epoxy groups and amino groups exist on the surface of the modified graphene, and the modified graphene reacts with ester groups in the PBAT at a high temperature in a double screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBAT and the graphene is improved, in addition, the original hydrogen bonds on the surface of the graphene assembled and modified by the chain extender can further generate ester bonds due to the high temperature, and the binding force between the graphene and the chain extender is improved.
< example 11>
The embodiment relates to a preparation method of graphene-degradable resin master batch, which specifically comprises the following steps
Respectively ultrasonically dispersing S1, 1g of graphene and 10g of SAG-008 in 200ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying a product to obtain the modified graphene. Due to the existence of hydroxyl and carboxyl on the surface of the graphene, SAG-008 is adsorbed on the surface of the graphene through a hydrogen bond effect to realize the assembly modification of the graphene.
S2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBS into a high-speed mixer, mixing for 3min, adding the mixture into a double screw, and performing melt water-cooling granulation to obtain the black master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the modified graphene is 0.5wt% of the PBS.
Epoxy groups and amino groups exist on the surface of the modified graphene, and the modified graphene reacts with ester groups in the PBS at a high temperature in the twin-screw to generate amido bonds and hydrogen bonds, so that the compatibility of the PBS and the graphene is improved, in addition, the original hydrogen bonds on the surface of the graphene assembled and modified by the chain extender can further generate ester bonds due to the high temperature, and the binding force of the graphene and the chain extender is improved.
< comparative example 1>
The invention provides a method for blow molding a graphene-degradable resin master batch into a film material, which comprises the following specific preparation steps: adding 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain master batches, wherein the temperature of the double screw is set to be 150-230 ℃, and the rotating speed is 15r/min. And adding the prepared master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the PBAT degradable film material.
< comparative example 2>
The invention provides a method for blow molding a graphene-degradable resin master batch into a film material, which comprises the following specific preparation steps:
and S1, 5g of graphene, 5g of antioxidant 1010 and 1000g of PBAT are added into a high-speed mixer, after mixing for 3min, the mixture is added into a double screw to carry out melt water-cooling granulation, so as to obtain black master batch, the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene accounts for 0.5wt% of the PBAT.
S2, adding the master batch into a film blowing machine, and obtaining the graphene-PBAT degradable mulching film material after melt extrusion, twice blowing, traction, curling and cooling
< comparative example 3>
The invention provides a method for blow molding a graphene-degradable resin master batch into a film material, which comprises the following specific preparation steps:
adding 5g of antioxidant 1010 and 1000g of PE into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain master batches, wherein the temperature of the double screw is set to be 150-230 ℃, and the rotating speed is 15r/min. And adding the master batch into a film blowing machine, and performing melt extrusion, twice blowing, traction, curling and cooling to obtain the PE mulching film material.
The membrane material prepared from the graphene-degradable resin master batch of the embodiment 1-4 and the membrane material prepared from the comparative example 1-3 are subjected to tensile property test with the test standard of GB/T13022-1991, the mulching film is cut into a square of 10 x 10cm and then buried under the ground at a depth of 10cm, and the transverse tensile load is tested after 180 days, and the test results are shown in the following table.
As can be seen from the above table, compared with the film materials of comparative examples 1 to 3, the film materials prepared from the graphene-PBAT degradable resin master batches of examples 1 to 4 have the advantages that the elongation at break and the breaking force are obviously increased and the mechanical strength is remarkably improved after the addition of graphene. In addition, compared with the traditional PE film material, the breaking force and the breaking elongation of the material are improved obviously, the main reason is that the chain extender is used as a bridge to connect the graphene and the PBAT degradable resin, the compatibility of the graphene and the PBAT resin is improved through the self-assembly of the chain extender on the surface of the graphene and the interaction between the graphene and PBAT resin groups self-assembled by the chain extender, and the interface between the graphene and the PABT resin matrix is tighter; in addition, the chain extender is self-assembled on the surface of the graphene, so that the interlayer spacing of the graphene is increased, PBAT resin molecules are easy to intercalate into the self-assembled graphene sheet layers in a molten composite state, the reaction between the self-assembled graphene and the PBAT resin groups is realized, the agglomeration of the graphene in the PBAT resin matrix is reduced, the enhancement effect of the graphene is exerted to the maximum, and the improvement of the toughness and the strength of the membrane material is realized. Compared with SAG-008, ADR-4370 has higher toughness, probably because amino and epoxy groups on SAG-008 are fully assembled on the surface of graphene and react between self-assembled graphene and PBAT resin, the interfacial compatibility is better, and the strength and elongation at break of the blown film are improved remarkably. Compared with the experiment 1 and the comparative example 1, the tensile strength of the graphene-PBAT mulching film and the tensile strength of the PBAT mulching film are respectively remained by 48.4% and 51.0% after degradation test, and the addition of the graphene does not influence the degradation performance of the PBAT.
The transverse and longitudinal fracture forces of the PBAT film material are respectively 0.80N and 1.00N, and compared with the common PBAT film material, the transverse and longitudinal fracture forces of the graphene-PBAT degradable film material are improved by 312 percent and 245 percent and respectively reach 3.30N and 3.35N; the transverse elongation at break and the longitudinal elongation at break of the PBAT film material are respectively 85% and 190%, and the elongation at break of the graphene-PBAT degradable film material is increased to 100% and 206%, which are respectively increased by 17.6% and 8.4%. The mechanical strength and the elongation at break of the PBAT film material are obviously improved by adding the graphene. In addition, after a degradable test, 51.0% and 48.4% of transverse tensile strength of the PBAT mulching film and the graphene-PBAT mulching film are respectively remained, which indicates that the degradable performance of the PBAT is not greatly influenced by adding the graphene.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, particular embodiments, but rather to those skilled in the art, and it is to be understood that the invention is capable of numerous modifications and that various changes may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (3)
1. The preparation method of the graphene-degradable resin master batch is characterized by comprising the following steps:
s1, preparing 200ml of DMF, respectively ultrasonically dispersing 1g of graphene and 10g of SAG-008 in DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing the SAG-008 under stirring, uniformly stirring, filtering, recovering the DMF, and freeze-drying a product to obtain modified graphene;
or respectively preparing 200ml and 100ml of DMF, respectively ultrasonically dispersing 1g of graphene and 5g of ADR-4370 in 200ml and 100ml of DMF, slowly adding the DMF solution containing the graphene into the DMF solution containing ADR-4370 under stirring, uniformly stirring, filtering, recovering DMF, and freeze-drying the product to obtain modified graphene;
s2, adding 5g of modified graphene, 5g of antioxidant 1010 and 1000g of PBAT into a high-speed mixer, mixing for 3min, adding the mixture into a double screw for melt water-cooling granulation to obtain the graphene-degradable master batch, wherein the temperature of the double screw is set to be 150-230 ℃, the rotating speed is 15r/min, and the graphene is 0.5wt% of the PBAT.
2. The graphene-degradable resin master batch is characterized by being prepared by the preparation method of the graphene-degradable resin master batch according to claim 1.
3. An application of the graphene-degradable resin master batch of claim 2 in preparing a degradable film material.
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