CN112048147A - Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof - Google Patents
Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
- C08K9/00—Use of pretreated ingredients
Abstract
The invention relates to an antibacterial and deodorant plastic master batch taking an elastomer as a carrier and a preparation method thereof, wherein the master batch comprises a rubber-plastic elastomer, deep oxidation modified graphene oxide, a composite antioxidant and a phase solvent POE-g-MAH, and the mass ratio of the components is 30-45: 30-45: 5-10: 5-10, wherein the deeply oxidized and modified graphene oxide is oxidized by using graphene oxide through microwave-induced ultraviolet irradiation. The invention takes an elastomer as a carrier, and mainly adopts the graphene oxide modified by deep oxidation, an antioxidant and a compatilizer to prepare master batches, provides terminal products for forming antibacterial/deodorant films, sheets, pipes, cables and the like by chemical processing, can be suitable for various common plastics such as PE, PP, EVA, PVC, PS and various PET and PA, has great application potential for spinning, leather, foaming and chemical forming processing, does not need a chemical method with potential pollution such as a strong oxidant and the like, and can provide very good antibacterial and deodorant effects.
Description
Technical Field
The invention relates to the technical field of plastic antibacterial materials, in particular to an antibacterial and deodorant plastic master batch taking an elastomer as a carrier and a preparation method thereof.
Background
Plastics have been used as materials with a wide range of applications in various fields of life, and therefore, the realization of the antibacterial effect thereof has wide demands and important significance. The antibacterial and deodorant material is a functional material which enables the material to have the capability of inhibiting or killing surface bacteria by adding a certain antibacterial and deodorant substance, but the antibacterial material is suitable for being added into plastic at present, and the antibacterial effect, toxicity, environmental protection, safety and combination effect with the plastic are not satisfactory.
The antibacterial performance of graphene and graphene oxide is excellent, the mechanism of sterilization/deodorization of graphene oxide is that the graphene oxide is in contact with bacteria, the cell membrane bears pressure, and the oxidation functional group and the membrane mutually generate oxidation, so that the graphene oxide punctures and cracks, RNA or DNA in the bacterial cell flows out to inactivate, in addition, the graphene oxide is added, the specific surface area is extremely large, and the specific surface area can reach 500-1000 m-2The odor adsorbing material has the advantages of strong adsorption capacity, excellent odor adsorbing and removing effects, excellent biocompatibility, toxicity, environmental protection and safety, and is one of antibacterial and deodorizing materials with great application potential. The graphene oxide and the graphene are two-dimensional lamellar carbon materials, the Young modulus of the graphene oxide and the graphene can reach 1.0TPa due to the six-membered ring rigid structure,the breaking strength can reach 130GPa, and the theoretical specific surface area is up to 20000m2Is an excellent functional material. However, when the filler is directly added into the preparation of plastics, the improvement effect on the rigidity, strength, toughness, ductility and the like of the plastics is insufficient due to the influence of the dispersibility of the filler in a matrix, an interface action and a space structure. Therefore, the graphene antibacterial material cannot be applied to the field of plastics.
Disclosure of Invention
The invention provides an antibacterial and deodorant master batch taking an elastomer as a carrier and a preparation method thereof, aiming at solving the technical problems that an antibacterial substance is not good enough in antibacterial and deodorant performance, not good in matching performance with a plastic carrier and not enough in comprehensive performance of an antibacterial material in the prior art.
The technical scheme of the invention is as follows:
the antibacterial/deodorant master batch with the elastomer as the carrier is characterized by comprising a rubber-plastic elastomer, deeply oxidized and modified graphene oxide, a composite antioxidant and a phase solvent POE-g-MAH, wherein the mass ratio of the components is 30-45: 30-45: 5-10: 5-10, wherein the deeply oxidized and modified graphene oxide is oxidized by using graphene oxide through microwave-induced ultraviolet irradiation.
Preferably, the rubber-plastic elastomer is any one or more of SBS, TPU, POE and EVA.
Further preferably, the rubber-plastic elastomer is SBS or POE.
Further preferably, the rubber-plastic elastomer is POE.
Preferably, the lubricant also comprises a dispersant internal lubricant zinc stearate and a lubricant polyethylene wax.
Further preferably, the deep oxidation modified graphene oxide crystal is characterized by disordered arrangement, and the ID/IG ratio is detected to be less than 1-1.2 on Raman spectrum.
The concentration of hydroxyl functional groups, carboxyl functional groups, epoxy functional groups and carbonyl functional groups of the deep oxidation modified graphene oxide crystal is preferably improved by 2-3 times compared with the average concentration of common graphene oxide.
Further preferably, the ultraviolet irradiation oxidation adopts a microwave electrodeless ultraviolet lamp module to emit 185mm ultraviolet rays, and the microwave frequency is 24.5GHZ or 950 MHZ.
Preferably, the composite antioxidant is prepared by mixing 1010 and 168 which are sold in the market according to the proportion of 2-3: 1.
The preparation method of the master batch is characterized in that the components are placed in an internal mixer, the internal mixer is used for mixing for 20-30mins at the temperature of 140 plus or minus 160 ℃, the mixed material is obtained and is put into a single-screw granulator, the temperature of the four sections is set to be 160 plus or minus 2 ℃, 165 plus or minus 2 ℃, 170 plus or minus 2 ℃, 165 plus or minus 2 ℃, the rotating speed is 340 plus or minus 360rpm, and the master batch is prepared in an air cooling mode after being granulated.
The invention has the beneficial technical effects that:
based on the graphene oxide sterilization/deodorization mechanism and the knowledge that the concentration of the oxidized functional group of the graphene oxide is controllable, the graphene oxide is irradiated by ultraviolet rays and air generated by microwaves, and UV/O3, wherein the oxidized functional group of the graphene oxide can be deepened by the secondary action of ozone in the process of irradiation, and the oxidized functional groups at different positions on the graphene can be changed differently under the action of the microwave temperature effect, so that the antibacterial performance of the deeply oxidized and modified graphene oxide is improved. On the basis, the invention takes the elastomer as a carrier, and mainly adopts the graphene oxide modified by deep oxidation, the antioxidant and the compatilizer to prepare the master batch, provides the terminal products for forming antibacterial/deodorant films, sheets, pipes, cables and the like by chemical processing, and is suitable for various common plastics such as PE, PP, EVA, PVC, PS and various PET and PA, has great application potential to spinning, leather, foaming and chemical forming processing, and does not need to use a chemical method with potential pollution such as a strong oxidant.
All the inorganic functional agent graphene can be dispersed and mixed with the carrier in advance, and the compatilizer is added, so that the inorganic functional agent graphene has compatibility with raw materials for reprocessing in advance. The elastomer is selected to avoid the functional additive from reducing the strength of the raw material due to the addition of the graphene oxide, for example: impact resistance while retaining the strength that it had originally.
The microwave power also becomes a controllable parameter, so the degree of deep oxidation modification can be controlled by controlling the microwave power, even if the C/O ratio of the graphene oxide subjected to deep oxidation modification reaches 45-50, the single crystal structure of the graphene oxide is not seriously damaged, and the ID/IG ratio is detected to be < 1-1.2 on a Raman spectrum. Mechanism of microwave induced ultraviolet ray: the microwave electrodeless ultraviolet lamp module is a novel light source based on the combination of two principles of fluorescent lamp gas discharge and high electromagnetic induction, a high-frequency generator generates high-frequency current when obtaining proper voltage, a high-frequency magnetic field is generated according to Faraday's law of electromagnetism, and inert gas in a bulb is ionized in avalanche mode under the action of the magnetic field to emit ultraviolet rays, and 185mm ultraviolet rays for generating ozone are adopted for carrying out further deep oxidation on graphene oxide.
The elastomer is a commercially available elastomer such as SBS, TPU, POE, EVA, etc., wherein SBS and POE are preferred, and POE is more preferred. POE is an elastomer polymerized from octene using metallocene as catalyst, which has outstanding mechanical properties of tensile strength, impact strength and toughness, and is used as toughening and low-temperature impact-resistant modifier.
The plastic master batch is a concentration rate prepared by loading a plastic functional auxiliary agent and a filler in a carrier resin in an ultra-constant manner and mixing the plastic functional auxiliary agent and the filler in advance. In the plastic processing and forming process, the components are added according to the required proportion to achieve the finished target.
The method for processing plastics by adopting the master batch has the following advantages:
uniformly dispersing: especially for the mixture of granular material and powder material, the functional assistants, pigment and stuffing with different shapes and shapes are difficult to disperse, and the mixture is first mixed and then pelletized before being processed and formed and then added into the whole formula.
Secondly, the cost is reduced: the concentrated granules are prepared and added into the formula for the second time, so that the addition amount is small, the loss rate is low, and the cost can be reduced.
Environmental protection and safety: the flying during the powder processing and manufacturing process is avoided, dust particles pollute the environment and even harm the health of people.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to specific examples.
Example 1
The graphene oxide subjected to deep oxidation modification is oxidized by using graphene oxide through microwave-initiated ultraviolet irradiation, 185mm ultraviolet rays are emitted by adopting a microwave electrodeless ultraviolet lamp module, and the microwave frequency is 24.5 GHZ.
The C/O ratio of the obtained graphene oxide subjected to deep oxidation modification is 45-50, the ID/IG ratio is less than 1-1.2 by detection on Raman spectrum, and the concentration of hydroxyl functional groups, carboxyl functional groups, epoxy functional groups and carbonyl functional groups is improved by 2-3 times compared with the average degree of common graphene oxide.
Mixing the components for 30mins at 150 ℃ by an internal mixer to obtain a mixed material, putting the mixed material into a single-screw granulator, setting the four-section temperature at 160 ℃, 165 ℃, 170 ℃, 165 ℃ and the rotating speed of 350rpm, granulating, and then carrying out air cooling to obtain the master batch.
By adopting the master batch, only 4 percent (1.4 percent of graphene oxide content) is needed to be added and mixed with the PET spinning raw material, the rupture strength of the produced PET fiber can keep the condition of GB standard 3.3N/d, and the sterilization condition of golden chain link bacteria and escherichia coli can reach 99.9 percent through test, and the master batch has the function of deodorization.
Example 2
The processing method is the same as above.
By adopting the master batch, only 5 percent (2.25 percent of graphene oxide content) is required to be added and mixed with ABS general plastic for extrusion, and the prepared forming container has the effects of sterilization of golden chain bacteria and escherichia coli by 99.9 percent and deodorization except that the mechanical condition of the original ABS is maintained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The antibacterial and deodorant plastic master batch with the elastomer as the carrier is characterized by comprising a rubber-plastic elastomer, deep oxidation modified graphene oxide, a composite antioxidant and a phase solvent POE-g-MAH, wherein the mass ratio of the components is 30-45: 30-45: 5-10: 5-10, wherein the deeply oxidized and modified graphene oxide is oxidized by using graphene oxide through microwave-induced ultraviolet irradiation.
2. The masterbatch of claim 1, wherein said rubber-plastic elastomer is any one or more of SBS, TPU, POE and EVA.
3. The masterbatch of claim 2 wherein said rubber-plastic elastomer is SBS or POE.
4. The masterbatch of claim 1, further comprising zinc stearate and polyethylene wax.
5. The masterbatch according to claim 1, wherein the deep oxidation modified graphene oxide has a C/O ratio of 45-50.
6. The masterbatch of claim 1, wherein the deep oxidation modified graphene oxide crystal is characterized by a disordered array, and the ID/IG ratio is < 1-1.2 as detected by Raman spectroscopy.
7. The master batch according to claim 1, wherein the concentration of the hydroxyl functional group, the carboxyl functional group, the epoxy functional group and the carbonyl functional group of the deep oxidation modified graphene oxide crystal is increased by 2-3 times compared with the average concentration of the common graphene oxide crystal.
8. The masterbatch of claim 1, wherein the ultraviolet irradiation oxidation employs a microwave electrodeless ultraviolet lamp module to emit 185mm ultraviolet light, and the microwave frequency is 24.5GHZ or 950 MHZ.
9. The master batch of claim 1, wherein the composite antioxidant is compounded by adopting antioxidants 1010 and 168 according to a ratio of 2-3: 1.
10. The method for preparing the master batch according to any one of claims 1 to 9, wherein the master batch is prepared by placing the components in an internal mixer, mixing the components for 20 to 30mins at the temperature of 140 ℃ and 160 ℃ by the internal mixer, feeding the obtained mixed material into a single-screw granulator, setting the four-stage temperature to 160 +/-2 ℃, 165 +/-2 ℃, 170 +/-2 ℃, 165 +/-2 ℃ and the rotating speed of 340 ℃ and 360rpm, and air-cooling the mixed material after granulating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010983577.4A CN112048147A (en) | 2020-09-18 | 2020-09-18 | Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof |
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| CN202010983577.4A CN112048147A (en) | 2020-09-18 | 2020-09-18 | Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof |
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