CN109054151B - Polyolefin flame-retardant composite material and preparation method thereof - Google Patents
Polyolefin flame-retardant composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyolefin flame-retardant composite material and a preparation method thereof, belonging to the technical field of polyolefin flame-retardant composite materials. The polyolefin flame-retardant composite material mainly comprises the following components in parts by weight: 0.1-5 parts of phosphorus-doped graphene, 0.1-25 parts of organic montmorillonite and 100 parts of polyolefin. According to the polyolefin flame-retardant composite material, the phosphorus-doped graphene and the organic montmorillonite are mixed in the polyolefin, and due to the physical isolation effect of the graphene sheet layer and the montmorillonite sheet layer, the contact of oxygen and the polyolefin can be remarkably inhibited, so that a better flame-retardant effect is achieved; phosphorus on the graphene sheet layer can promote carbon formation, so that the introduction of phosphorus-doped graphene and organic montmorillonite can well improve the flame retardant property of polyolefin. In addition, the polyolefin flame-retardant composite material disclosed by the invention is low in toxicity and smoke, meets the environmental protection requirement, and has a good development prospect.
Description
Technical Field
The invention relates to a polyolefin flame-retardant composite material and a preparation method thereof, belonging to the technical field of polyolefin flame-retardant composite materials.
Background
Polyolefins are widely used in various aspects of life due to their excellent mechanical properties, chemical stability and easy processability, but since polyolefins are composed of two elements, carbon and hydrogen, such chemical structures make them easily combustible and release a large amount of toxic gases and fumes. For example, Low Density Polyethylene (LDPE) is widely applied to the field of material processing due to good hot processability, but pure LDPE materials are easy to burn, generate a large amount of heat and molten drops in the combustion process, and have high flame propagation speed and are not easy to extinguish. Since the use of polyolefins represented by LDPE is limited due to their flammability, the improvement of the flame retardant property of polyolefins is a necessary way to expand the use thereof. At present, the flame retardant performance of LDPE polyolefin is improved by adding halogen flame retardant, and although the flame retardant effect is good, a large amount of toxic gas is released in the flame retardant process.
Disclosure of Invention
The invention aims to provide a low-toxicity polyolefin flame-retardant composite material.
The invention also provides a preparation method of the polyolefin flame-retardant composite material.
In order to achieve the purpose, the technical scheme adopted by the polyolefin flame-retardant composite material is as follows:
a polyolefin flame-retardant composite material mainly comprises the following components in parts by weight: 0.1-5 parts of phosphorus-doped graphene, 0.1-25 parts of organic montmorillonite and 100 parts of polyolefin.
According to the polyolefin flame-retardant composite material, the phosphorus-doped graphene and the organic montmorillonite are mixed in the polyolefin, and due to the physical isolation effect of the montmorillonite and the graphene sheet layer, the contact of oxygen and the polyolefin can be remarkably inhibited, so that the polyolefin flame-retardant composite material has a good flame-retardant effect; phosphorus on the graphene sheet layer can promote carbon formation, and phosphorus-doped graphene and organic montmorillonite can well improve the flame retardant property of polyolefin. In addition, the polyolefin flame-retardant composite material disclosed by the invention is low in toxicity and smoke, meets the environmental protection requirement, and has a good development prospect.
Preferably, the polyolefin flame-retardant composite material mainly comprises the following components in parts by weight: 1-5 parts of phosphorus-doped graphene, 5-25 parts of organic montmorillonite and 100 parts of polyolefin.
Preferably, the mass of the organic montmorillonite is 1-5 times of that of the phosphorus-doped graphene.
Preferably, the polyolefin is at least one of low density polyethylene, high density polyethylene and polypropylene.
Preferably, the polyolefin flame-retardant composite material further comprises a compatilizer and an antioxidant; the mass ratio of the compatilizer to the antioxidant to the polyolefin is 2-4: 0.5-2: 100.
Preferably, the compatilizer is at least one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene. The type of compatibilizer may be preferred with respect to the polyolefin, such as polyethylene, maleic anhydride grafted polyethylene, and maleic anhydride grafted polypropylene if the polyolefin is polypropylene.
Preferably, the antioxidant is at least one of phosphite antioxidant and multi-hindered phenol antioxidant.
Preferably, the phosphorus-doped graphene is prepared by a method comprising the following steps: dispersing graphene oxide sponge in concentrated phosphoric acid, carrying out ultrasonic treatment, then carrying out heat preservation at 80-100 ℃, carrying out solid-liquid separation, washing the obtained solid phase, and then placing the washed solid phase in a protective atmosphere for carrying out heat preservation treatment at 350-450 ℃ to obtain the graphene oxide sponge.
Preferably, before solid-liquid separation, water is added into the system obtained after heat preservation at 80-100 ℃ for washing. When water is added for washing, water may be added in portions. The distilled water is added in batches so that the washing effect can be increased by adding a small amount of distilled water for many times. The unreacted phosphoric acid can be removed by adding water for washing and carrying out solid-liquid separation.
Compared with graphene oxide powder and the like, the graphene oxide sponge is easier to ultrasonically strip and disperse, so that the preparation of single-layer phosphorus-doped graphene is facilitated. Preferably, the volume of the concentrated phosphoric acid adopted for each 1g of the graphene oxide sponge is 200-600 mL. Optionally, the mass fraction of the concentrated phosphoric acid is 80-86%.
In the preparation method of the phosphorus-doped graphene, graphene oxide with phosphoric acid adsorbed on the surface is obtained after heat preservation treatment at 80-100 ℃; and (3) the solid phase is subjected to heat preservation treatment in a protective atmosphere, so that oxygen-containing groups in the graphene oxide can be removed, and the phosphorus-doped graphene can be obtained. According to the invention, phosphorus atoms are introduced into the surface of the phosphorus-doped graphene prepared by taking the graphene oxide sponge as a raw material, and the carbon formation of the composite material during high-temperature combustion can be promoted due to the carbon formation promoting effect of phosphorus, so that the flame retardant effect is improved.
Preferably, the time of ultrasonic treatment is 30-60 min.
Preferably, the heat preservation time is 4-12 h at 80-100 ℃.
Preferably, the protective atmosphere is nitrogen.
Preferably, the time for heat preservation treatment at 350-450 ℃ is 2-6 h.
The preparation method of the polyolefin flame-retardant composite material adopts the technical scheme that:
the preparation method of the polyolefin flame-retardant composite material comprises the following steps: providing a mixed dispersion liquid of phosphorus-doped graphene, organic montmorillonite and polyolefin in an organic solvent, then casting the mixed dispersion liquid, and drying to obtain the phosphorus-doped graphene/organic montmorillonite/polyolefin composite material.
The preparation method of the polyolefin flame-retardant composite material adopts a solvent dispersion method, realizes the uniform dispersion of the doped graphene and the organic montmorillonite in the polyolefin matrix, and greatly improves the flame-retardant property of the polyolefin composite material.
Preferably, the organic solvent is at least one of xylene and trichlorobenzene. Compared with other solvents, the xylene as the organic solvent has the beneficial effect of low toxicity.
Preferably, the drying temperature is 40-60 ℃.
Preferably, the method for preparing the mixed dispersion comprises the following steps: firstly, uniformly dispersing phosphorus-doped graphene and organic montmorillonite in an organic solvent, then carrying out ultrasonic treatment, and then adding polyolefin for dissolution to obtain the graphene-montmorillonite composite material.
In the preparation method of the mixed dispersion liquid, the ultrasonic treatment is used for promoting the stripping and dispersion of the phosphorus-doped graphene and the organic montmorillonite in the solvent.
The phosphorus-doped graphene and the organic montmorillonite are uniformly dispersed in the organic solvent, namely the phosphorus-doped graphene and the organic montmorillonite are added into the organic solvent and mechanically stirred for 2-4 hours at the rotating speed of 100-300 r/min.
And when the mixed dispersion liquid is prepared, the ultrasonic treatment time is 30-60 min.
In the preparation of the mixed dispersion, the polyolefin may be added and then the system may be heated in order to disperse the polyolefin uniformly in the system. The heating is to raise the temperature of the system to 120-140 ℃ and keep the temperature for 30-60 min. Preferably, the system is heated while stirring is continued.
Drawings
Fig. 1 is an SEM image of the polyolefin flame retardant composite in example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The organic montmorillonite adopted in the specific embodiment has the brand number of DK-1N, and is obtained by treating raw soil with cetyl trimethyl ammonium bromide, Zhejiang Fenghong clay chemical Co.
Example 1
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 1 part of phosphorus-doped graphene, 5 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin is Low Density Polyethylene (LDPE) with a density of 0.92g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The preparation method of the polyolefin flame-retardant composite material of the embodiment comprises the following steps:
1) preparing phosphorus-doped graphene: adding 1g of freeze-dried graphene oxide sponge into a single-neck flask, then adding 200mL of 85% concentrated phosphoric acid, ultrasonically dispersing for 30min, heating to 80 ℃ under magnetic stirring, preserving heat and magnetically stirring for 12 h; then transferring the product system into a big beaker, adding 1L of distilled water for washing, then carrying out suction filtration by adopting a filter membrane with the aperture of 0.22 mu m to remove unreacted phosphoric acid, placing a filter cake into a muffle furnace, introducing nitrogen, then raising the temperature of the muffle furnace to 350 ℃, and reacting for 6 hours to obtain phosphorus-doped graphene;
2) adding 0.1g of phosphorus-doped graphene prepared in the step 1) and 0.5g of organic montmorillonite into 200mL of xylene, magnetically stirring at the rotating speed of 100r/min for 4 hours, then ultrasonically dispersing for 30 minutes, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 120 ℃, and stirring for 30 minutes to obtain a mixed dispersion liquid;
3) pouring the mixed dispersion liquid obtained in the step 2) into a mold, and placing the mold in an oven to be dried at 40 ℃ to obtain the nano-composite material.
The polyolefin flame-retardant composite material of the embodiment is subjected to SEM test, the obtained SEM image is shown in figure 1, and it can be seen from figure 1 that the nano flame retardant phosphorus-doped graphene and the organic montmorillonite are uniformly dispersed in a polyolefin system, and the agglomeration phenomenon of graphene and montmorillonite sheets is not found, so that the flame-retardant effect of the composite material is favorably improved.
Example 2
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 3 parts of phosphorus-doped graphene, 15 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin is Low Density Polyethylene (LDPE) with a density of 0.92g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The preparation method of the polyolefin flame-retardant composite material of the embodiment comprises the following steps:
1) preparing phosphorus-doped graphene: adding 1g of freeze-dried graphene oxide sponge into a single-neck flask, adding 300mL of 85% concentrated phosphoric acid, performing ultrasonic dispersion for 30min, heating to 90 ℃ under magnetic stirring, preserving heat, and performing magnetic stirring for 10 h; then transferring the product system into a big beaker, adding 1L of distilled water to wash the product, then carrying out suction filtration by adopting a filter membrane with the aperture of 0.22 mu m to remove unreacted phosphoric acid, placing a filter cake into a muffle furnace, introducing nitrogen, then raising the temperature of the muffle furnace to 400 ℃, and reacting for 5 hours to obtain phosphorus-doped graphene;
2) adding 0.3g of phosphorus-doped graphene prepared in the step 1) and 1.5g of organic montmorillonite into 200mL of xylene, magnetically stirring at the rotating speed of 250r/min for 3 hours, then ultrasonically dispersing for 30 minutes, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 140 ℃, and stirring for 30 minutes to obtain a mixed dispersion liquid;
3) pouring the mixed dispersion liquid obtained in the step 2) into a mold, and placing the mold in an oven to be dried at 40 ℃ to obtain the nano-composite material.
Example 3
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 0.1 part of phosphorus-doped graphene, 0.5 part of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin is Low Density Polyethylene (LDPE) with a density of 0.92g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The preparation method of the polyolefin flame-retardant composite material of the embodiment comprises the following steps:
1) preparing phosphorus-doped graphene: adding 1g of freeze-dried graphene oxide sponge into a single-neck flask, adding 400mL of 85% concentrated phosphoric acid, performing ultrasonic dispersion for 30min, heating to 100 ℃ under magnetic stirring, preserving heat, and performing magnetic stirring for 8 h; then transferring the product system into a big beaker, adding 1L of distilled water for washing, then carrying out suction filtration by adopting a filter membrane with the aperture of 0.22 mu m to remove unreacted phosphoric acid, placing a filter cake into a muffle furnace, introducing nitrogen, then raising the temperature of the muffle furnace to 450 ℃, and reacting for 2 hours to obtain phosphorus-doped graphene;
2) adding 0.01g of phosphorus-doped graphene prepared in the step 1) and 0.05g of organic montmorillonite into 200mL of xylene, magnetically stirring at the rotating speed of 300r/min for 2 hours, then ultrasonically dispersing for 30 minutes, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 120 ℃, and stirring for 30 minutes to obtain a mixed dispersion liquid;
3) pouring the mixed dispersion liquid obtained in the step 2) into a mold, and placing the mold in an oven to be dried at 50 ℃ to obtain the nano-composite material.
Example 4
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 5 parts of phosphorus-doped graphene, 25 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin is Low Density Polyethylene (LDPE) with a density of 0.92g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The preparation method of the polyolefin flame-retardant composite material of the embodiment comprises the following steps:
1) preparing phosphorus-doped graphene: adding 1g of freeze-dried graphene oxide sponge into a single-neck flask, adding 600mL of 85% concentrated phosphoric acid, ultrasonically dispersing for 60min, heating to 90 ℃ under magnetic stirring, preserving heat and magnetically stirring for 4 h; then transferring the product system into a big beaker, adding 1L of distilled water to wash the product, then carrying out suction filtration by adopting a filter membrane with the aperture of 0.22 mu m to remove unreacted phosphoric acid, placing a filter cake into a muffle furnace, introducing nitrogen, then raising the temperature of the muffle furnace to 400 ℃, and reacting for 5 hours to obtain phosphorus-doped graphene;
2) adding 0.3g of phosphorus-doped graphene prepared in the step 1) and 1.5g of organic montmorillonite into 200mL of xylene, magnetically stirring at the rotating speed of 250r/min for 3 hours, then ultrasonically dispersing for 60 minutes, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 140 ℃, and stirring for 30 minutes to obtain a mixed dispersion liquid;
3) pouring the mixed dispersion liquid obtained in the step 2) into a mold, and placing the mold in an oven to be dried at 60 ℃ to obtain the nano-composite material.
Example 5
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 5 parts of phosphorus-doped graphene, 5 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin is Low Density Polyethylene (LDPE) with a density of 0.92g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The preparation method of the polyolefin flame-retardant composite material of the embodiment comprises the following steps:
1) preparing phosphorus-doped graphene: adding 1g of freeze-dried graphene oxide sponge into a single-neck flask, adding 500mL of 85% concentrated phosphoric acid, performing ultrasonic dispersion for 40min, heating to 80 ℃ under magnetic stirring, preserving heat, and performing magnetic stirring for 6 h; then transferring the product into a big beaker, adding 1L of distilled water for washing, then carrying out suction filtration by adopting a filter membrane with the aperture of 0.22 mu m to remove unreacted phosphoric acid, placing a filter cake into a muffle furnace, introducing nitrogen, then raising the temperature of the muffle furnace to 400 ℃, and reacting for 3 hours to obtain phosphorus-doped graphene;
2) the phosphorus-doped graphene prepared in the step 1) is adopted to prepare the polyolefin flame-retardant composite material according to the methods of the steps 2) to 3) in the embodiment 1.
Example 6
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 5 parts of phosphorus-doped graphene, 5 parts of organic montmorillonite, 2 parts of compatilizer, 2 parts of antioxidant and 100 parts of polyolefin; the polyolefin is High Density Polyethylene (HDPE) with a density of 0.95g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polyethylene; the antioxidant is phosphite antioxidant.
The flame retardant polyolefin composite material of this example was prepared in exactly the same manner as in example 1, except that the amount of the compatibilizer and the antioxidant used were different from the amount of the polyolefin used.
Example 7
The polyolefin flame-retardant composite material of the embodiment comprises the following components in parts by weight: 5 parts of phosphorus-doped graphene, 5 parts of organic montmorillonite, 4 parts of compatilizer, 0.5 part of antioxidant and 100 parts of polyolefin; the polyolefin is polypropylene, and the density of the polypropylene is 0.90g/cm3(ii) a The adopted compatilizer is maleic anhydride grafted polypropylene; the antioxidant is phosphite antioxidant.
The flame retardant polyolefin composite material of this example was prepared in exactly the same manner as in example 1, except that the amount of the compatibilizer and the antioxidant used were different from the amount of the polyolefin used.
Comparative example 1
The polyolefin flame-retardant composite material of the comparative example consists of the following components in parts by weight: 5 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin was Low Density Polyethylene (LDPE) as in example 1.
The preparation method of the polyolefin flame-retardant composite material of the comparative example comprises the following steps:
1) adding 0.5g of organic montmorillonite into 200mL of dimethylbenzene, performing magnetic stirring for 4 hours, performing ultrasonic dispersion for 30min, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 120 ℃, and stirring for 30min to obtain a mixed dispersion liquid;
2) pouring the mixed dispersion liquid obtained in the step 1) into a mold, and placing the mold in an oven to dry at 40 ℃ to obtain the product.
Comparative example 2
The polyolefin flame-retardant composite material of the comparative example consists of the following components in parts by weight: 1 part of graphene, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin and graphene used were exactly the same as in example 1.
The preparation method of the polyolefin flame-retardant composite material of the comparative example comprises the following steps:
1) adding 0.1g of graphene into 200mL of dimethylbenzene, magnetically stirring for 4 hours, then ultrasonically dispersing for 30min, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 120 ℃, and stirring for 30min to obtain a mixed dispersion liquid;
2) pouring the mixed dispersion liquid obtained in the step 1) into a mold, and placing the mold in an oven to dry at 40 ℃ to obtain the product.
Comparative example 3
The polyolefin flame-retardant composite material of the comparative example consists of the following components in parts by weight: 1 part of graphene, 5 parts of organic montmorillonite, 3 parts of compatilizer, 1 part of antioxidant and 100 parts of polyolefin; the polyolefin and graphene used were exactly the same as in example 1.
The preparation method of the polyolefin flame-retardant composite material of the comparative example comprises the following steps:
1) adding 0.1g of graphene and 0.5g of organic montmorillonite into 200mL of dimethylbenzene, magnetically stirring for 4 hours, then ultrasonically dispersing for 30min, then adding 10g of low-density polyethylene, 0.3g of maleic anhydride grafted polyethylene and 0.1g of phosphite antioxidant, heating to 120 ℃, and stirring for 30min to obtain a mixed dispersion liquid;
2) pouring the mixed dispersion liquid obtained in the step 1) into a mold, and placing the mold in an oven to dry at 40 ℃ to obtain the product.
Examples of the experiments
The polyolefin flame-retardant composite materials of examples 1 to 7 and comparative examples 1 to 3 were each placed in a press vulcanizer at 150 ℃ and pressed for 8 minutes, and then the pressed sample plate was cut into a 120X 6X 3mm sample strip, and the oxygen index thereof was measured.
The results of the flame retardant tests of the polyolefin flame retardant composite materials of examples 1 to 7 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 flame retardant test results
The flame retardant test results in table 1 show that the limited oxygen index of the polyolefin flame retardant composite material is 19.5-29.3%, and the polyolefin flame retardant composite material has a good flame retardant effect.
Claims (9)
1. A polyolefin flame retardant composite characterized by: the paint mainly comprises the following components in parts by weight: 0.1-5 parts of phosphorus-doped graphene, 0.1-25 parts of organic montmorillonite and 100 parts of polyolefin; the phosphorus-doped graphene is prepared by a method comprising the following steps: dispersing graphene oxide sponge in concentrated phosphoric acid, carrying out ultrasonic treatment, then carrying out heat preservation at 80-100 ℃, carrying out solid-liquid separation, washing the obtained solid phase, and then placing the washed solid phase in a protective atmosphere for carrying out heat preservation treatment at 350-450 ℃ to obtain the graphene oxide sponge.
2. The polyolefin flame retardant composite of claim 1 wherein: the paint mainly comprises the following components in parts by weight: 1-5 parts of phosphorus-doped graphene, 5-25 parts of organic montmorillonite and 100 parts of polyolefin.
3. The polyolefin flame retardant composite of claim 1 wherein: the mass of the organic montmorillonite is 1-5 times of that of the phosphorus-doped graphene.
4. The polyolefin flame retardant composite of claim 1 wherein: the polyolefin is at least one of low-density polyethylene, high-density polyethylene and polypropylene.
5. The polyolefin flame retardant composite of claim 1 wherein: also comprises a compatilizer and an antioxidant; the mass ratio of the compatilizer to the antioxidant to the polyolefin is 2-4: 0.5-2: 100.
6. The polyolefin flame retardant composite of claim 5 wherein: the compatilizer is at least one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; the antioxidant is at least one of phosphite antioxidant and multi-component hindered phenol antioxidant.
7. The polyolefin flame retardant composite of claim 1 wherein: the volume of concentrated phosphoric acid adopted by every 1g of graphene oxide sponge is 200-600 mL.
8. A method of preparing a polyolefin flame retardant composite as claimed in claim 1, wherein: the method comprises the following steps: providing a mixed dispersion liquid of phosphorus-doped graphene, organic montmorillonite and polyolefin in an organic solvent, then casting the mixed dispersion liquid, and drying to obtain the phosphorus-doped graphene/organic montmorillonite/polyolefin composite material.
9. The method of claim 8, wherein: the preparation method of the mixed dispersion liquid comprises the following steps: firstly, uniformly dispersing phosphorus-doped graphene and organic montmorillonite in an organic solvent, then carrying out ultrasonic treatment, and then adding polyolefin for dissolution to obtain the graphene-montmorillonite composite material.
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Effective date of registration: 20230412 Address after: 471800 Intersection of Jingjin Road and Weiyi Road, Luoxin Park, Xin'an County Economic and Technological Development Zone, Luoyang City, Henan Province Patentee after: Luoyang Meizuan New Material Co.,Ltd. Address before: 471003 No. 48, Xiyuan Road, Jianxi District, Henan, Luoyang Patentee before: HENAN University OF SCIENCE AND TECHNOLOGY |