CN115160645B - Preparation method of vermiculite compound flame retardant material - Google Patents
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Abstract
The invention discloses a preparation method of a vermiculite compound flame-retardant material, which comprises vermiculite, carbon nano tubes, boron phosphate and tin hydroxide. The preparation method of the invention prepares the vermiculite carbon nano tube composite material by preprocessing vermiculite, prepares the vermiculite flame-retardant material by crystallization treatment, mixes the vermiculite flame-retardant material with organic plastic material, and adds curing agent to prepare the plastic finished product with high flame-retardant property. The method for preparing the flame-retardant material has simple process and easy popularization, utilizes the vermiculite laminate structure, inserts the organic and inorganic flame retardants, realizes the compounding of various flame retardants, constructs the high-performance flame-retardant material, and has certain infrared and ultraviolet blocking capability besides the flame retardant performance, thus being suitable for large-scale popularization.
Description
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a preparation method of a vermiculite compound flame retardant material.
Background
Vermiculite is one of nonmetallic minerals with better resource prospect and potential advantage in China, is an important nonmetallic mineral, is also a magnesium-containing water aluminum silicate secondary metamorphic mineral with a layered structure, belongs to layered silicate, and is low in cost and easy to obtain. The vermiculite is high-temperature resistant and has good electrical insulation property; expanded vermiculite is prone to water absorption and hygroscopicity; swelling at high temperature and easy peeling. Vermiculite has the characteristics of better interlayer cation exchange capacity, expansibility, adsorption capacity, sound insulation, heat insulation, fire resistance, freezing resistance and the like, has stable chemical properties, is insoluble in water, is nontoxic, tasteless and free of side effects, and is mainly used for treating waste water containing heavy metals and organic cations, preparing antibacterial materials and heat insulation materials, vermiculite filter aids, purifying agents, organic vermiculite and the like by utilizing the good adsorption performance and ion exchange performance of the vermiculite.
At present, the vermiculite in China is almost used for building heat insulation materials after being prepared into expanded vermiculite, the value is very low, an industrial chain for effectively utilizing vermiculite resources is not established, and compared with foreign countries, the development and utilization of the vermiculite in China have the following problems: 1) The application range is narrow: the application of the domestic vermiculite is mainly limited to building materials, and has a small amount of application in agriculture, electromechanics, chemical industry and environmental protection. Besides the five industrial departments, the method is also applied to the mechanical, electronic and metallurgical industries, and has obviously wide application fields. 2) The product varieties are few: the varieties of vermiculite patent products in China are obviously less than those in foreign countries, and the gap between the varieties in the field of agricultural building materials and petrochemical industry is also great. 3) The processing method is simple: the vermiculite in China is generally utilized directly by raw ore, and is utilized after being calcined and expanded. Different processing methods are often adopted for different applications abroad, and the processing technical method is advanced, novel and various, so that the widening of the utilization field and the development of new products are correspondingly promoted. 4) The utilization rate of fine vermiculite is low: the application of coarse-grained vermiculite in China has a good foundation, but the utilization rate of fine-grained vermiculite with granularity smaller than 0.3mm is low, so that resource waste is caused. Advanced vermiculite processing techniques are difficult to introduce directly from abroad in view of international technical trade barriers and intellectual property protection. From the sustainable development point of view, the research on deep processing technology and application technology of vermiculite must be enhanced at present, the industrial innovation is accelerated, and novel functionalized new materials are prepared, so that new vermiculite products with higher added values are obtained.
Polymer materials such as EVA, PP, PE and PVC have great influence on social development and life of people, and flame retardance of polymer ion materials has been attracting attention since last century, and people have improved flame retardance by adding substances which are flame retardants, which can terminate combustion reactions by chemical action when they are not combusted or combusted, to polymer materials to prepare composite materials by utilizing high compatibility of polymer high molecular materials. Epoxy resins are widely used as base resins for electronic laminates, packaging materials, electronic and electrical components and coatings, and flammable epoxy resins must be flame retardant in order to ensure fire safety in applications. Although the halogen flame retardant has high flame retardant efficiency, the flame retardant material can release a large amount of smoke, toxic and corrosive gases during combustion, and is harmful to human bodies and the environment. For this reason, research on new materials that are environmentally friendly and highly efficient in flame retardance has become a trend in the flame retardant field.
Therefore, combining the problems, the preparation method of the vermiculite compound flame retardant material is provided, and the problems are needed to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the invention provides a preparation method of the vermiculite compound flame retardant material, and the vermiculite compound flame retardant material prepared by the method has high stability and good flame retardant effect, and the preparation method of the flame retardant material has simple process, is easy to popularize and has obvious economic value.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the vermiculite compound flame-retardant material comprises the following steps:
s1, preprocessing vermiculite: calcining raw ore vermiculite to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after washing flotation; shearing and crushing the prepared expanded vermiculite to 100-10000 meshes by a crusher, soaking vermiculite powder in 20% -30% ferric chloride solution, performing iron modification for 1-56h at the rotating speed of 100-20000rpm, wherein the volume ratio of the vermiculite to the ferric chloride solution is 1:5-15, washing and drying at the modification reaction temperature of 25-100 ℃, and standing the treated modified vermiculite powder;
s2, preparing a vermiculite carbon nano tube composite material: uniformly mixing the modified vermiculite powder obtained in the step S1 with a carbon source by ultrasonic boiling, putting the mixture into a high-temperature tube furnace reactor, introducing inert gas, and reacting at the temperature of 600-1000 ℃ at the heating rate of 1-20 ℃/min to obtain a non-agglomerated vermiculite/carbon nano tube composite material;
s3, preparing a vermiculite flame retardant material: putting the vermiculite/carbon nano tube composite material obtained in the step S2 into a hydrothermal kettle, firstly adding 0.0001-0.1mol/L boric acid and sodium pyrophosphate, stirring for 5-100min, then adding 0.0001-0.01mol/L sulfanilic acid, wherein the volume ratio of the vermiculite/carbon nano tube composite material to the mixed liquid of the boric acid, the sodium pyrophosphate and the sulfanilic acid is 1:20-40, stirring uniformly, dropwise adding 1-30ml of 0.0001-0.01mol/L stannous chloride, adding 0.01-10.0g urea after the dropwise adding, crystallizing at the temperature of 80-200 ℃ for 1-48h, washing and drying to obtain the vermiculite compound flame retardant material for later use;
s4, mixing organic plastic materials: dispersing the vermiculite compound flame retardant material obtained in the step S3 in an absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite compound flame retardant material to the absolute ethyl alcohol solution is 1:5-15, uniformly stirring, ultrasonically assisted centrifugally washing for 3-5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging, and drying to obtain a mixture of the vermiculite compound flame retardant material and the organic plastic material;
s5, preparing a finished product vermiculite compound flame retardant material: and (3) adding a curing agent into the mixture of the vermiculite flame retardant material and the organic plastic material obtained in the step (S4), and performing heat treatment and molding to obtain the plastic product with high flame retardant property.
Preferably, the ferric chloride solution in the step S1 may also be a cobalt chloride solution or a nickel chloride solution.
Preferably, the calcination temperature in the step S1 is 550-900 ℃ and the calcination time is 1-100min; the shearing and crushing time of the crusher is 1-200min, the rotating speed is 1000-20000rpm, the reaction time is 1-48h, the drying temperature is 40-180 ℃ and the drying time is 0.5-24h.
Preferably, the carbon source in step S2 includes, but is not limited to, melamine, pyridine, pyrrole, dicyandiamide.
Preferably, the sulfanilic acid in the step S3 may be amino acid, DOPO or maleic acid.
Preferably, the step S4 is carried out by stirring for 1-55min at 500-1800rpm after mixing with the organic plastic material.
Preferably, the organic plastic material in the step S4 includes, but is not limited to, ethylene oxide, propylene oxide, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polyurethane.
Preferably, in the step S5, the mass ratio of the mixture of the vermiculite flame retardant material and the organic plastic material to the curing agent is 2-5:5.
preferably, the heat treatment molding condition in the step S5 is that the set temperature is 100-300 ℃ and the treatment time is 1-100min.
Preferably, the curing agent in the step S5 includes, but is not limited to, ethylene oxide, propylene oxide, glycerin, dioctyl phthalate.
Compared with the prior art, the invention has the following beneficial effects:
according to the technical scheme, vermiculite is used as a main base material, the vermiculite is used as a layered material and mainly consists of elements such as silicon, magnesium and aluminum, organic and inorganic flame retardants are inserted between vermiculite laminates or layers, the compounding of various flame retardants is realized, a high-performance three-dimensional flame retardant is constructed, carbon nano tubes are grown on the vermiculite laminates, an intercalated multi-level structure flame retardant is constructed by a coprecipitation method, a composite flame retardant material is prepared, the surface modification and preparation of fine-particle vermiculite are realized, and a finished product has certain infrared and ultraviolet blocking capability besides the flame retardant performance. The invention constructs a novel flame-retardant material by a synthetic method and provides a new thought for the preparation research of developed vermiculite flame-retardant material.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
calcining raw ore vermiculite at 900 ℃ to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after washing flotation; the prepared expanded vermiculite is sheared and crushed for 10min to 650 meshes at 10000rpm, 2g of vermiculite powder is taken and soaked in 30ml of 30% ferric chloride solution, the reaction is carried out for 24h at 4000rpm, the reaction temperature is 40 ℃, the reaction is carried out for 3 times by washing with deionized water, and the drying treatment is carried out for 18h at 125 ℃.
And (3) uniformly mixing the iron modified vermiculite powder and 2g of melamine by ultrasonic boiling, putting the mixture into a high-temperature tubular furnace reactor, introducing inert gas, heating to 700 ℃ at a heating rate of 5 ℃/min, and reacting for 2 hours to obtain the vermiculite carbon nanotube composite material.
Putting the vermiculite carbon nano tube composite material into a hydrothermal kettle, firstly adding 0.001mol/L boric acid and sodium pyrophosphate, stirring for 15min, then adding 0.0001mol/L sulfanilic acid, wherein the volume ratio of the vermiculite carbon nano tube composite material to the mixed liquid of boric acid, sodium pyrophosphate and sulfanilic acid is 1:40, uniformly stirring, dropwise adding 10ml of 0.001mol/L stannous chloride, adding 1.2g of urea after the dropwise adding, setting the temperature to be 110 ℃, crystallizing for 24h, washing with deionized water, and drying to obtain the vermiculite composite flame retardant material.
Putting the vermiculite composite flame retardant material into an absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite composite flame retardant material to the absolute ethyl alcohol solution is 1:10, uniformly stirring, ultrasonically assisted centrifugally washing for 5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging at 1000rpm for 10min for separation, and drying at 60 ℃ for 24h to obtain the mixture of the vermiculite flame retardant material and the organic plastic material.
Mixing vermiculite flame retardant material and PVC plastic material, adding DOP, wherein the mass ratio of the mixture of the vermiculite flame retardant material and the PVC plastic material to the curing agent is 1:1, performing hot pressing treatment at 180 ℃ to obtain the vermiculite compound flame retardant material with high flame retardant property. The limiting oxygen index LOI is up to 35.4%.
Example 2:
pretreatment of vermiculite: calcining raw ore vermiculite at 900 ℃ to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after washing flotation; the prepared expanded vermiculite is sheared and crushed to 700 meshes, 2g of vermiculite powder is taken and soaked in 30ml of 30% ferric chloride solution, the reaction is carried out for 24 hours at the rotating speed of 3000rpm, the reaction temperature is 40 ℃, the deionized water is used for washing 3 times after the reaction, and the drying treatment is carried out for 20 hours at the temperature of 130 ℃.
And (3) uniformly mixing the iron modified vermiculite powder and 1.5g dicyandiamide by ultrasonic boiling, putting the mixture into a high-temperature tubular furnace reactor, introducing inert gas, heating to 760 ℃ at a heating rate of 5 ℃/min, and reacting for 2 hours to obtain the vermiculite carbon nanotube composite material.
Putting the vermiculite carbon nano tube composite material into a hydrothermal kettle, firstly adding 0.001mol/L boric acid and sodium pyrophosphate, stirring for 15min, then adding 0.0001mol/L sulfanilic acid, wherein the volume ratio of the vermiculite carbon nano tube composite material to the mixed liquid of the boric acid, the sodium pyrophosphate and the sulfanilic acid is 1:40, uniformly stirring, dropwise adding 10ml of 0.001mol/L stannous chloride, adding 1.2g of urea after the dropwise adding, setting the temperature to be 110 ℃, crystallizing for 24h, washing with deionized water for 3 times, and drying at the temperature of 60 ℃ for 24h to obtain the vermiculite composite flame retardant material.
Dispersing a vermiculite composite flame retardant material in an absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite composite flame retardant material to the absolute ethyl alcohol solution is 1:10, uniformly stirring, ultrasonically assisted centrifugally washing for 5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging at 1000rpm for 10min for separation, and drying at 60 ℃ for 24h to obtain the mixture of the vermiculite flame retardant material and the organic plastic material.
Mixing vermiculite flame retardant material and PVC plastic material, adding DOP, wherein the mass ratio of the mixture of the vermiculite flame retardant material and the PVC plastic material to the curing agent is 1:1, performing hot pressing treatment at 190 ℃ to obtain the vermiculite compound flame retardant material with high flame retardant property. The limiting oxygen index LOI is up to 35.4%.
Example 3:
calcining raw ore vermiculite at 900 ℃ to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after water washing and flotation; the prepared expanded vermiculite is sheared and crushed for 15min to 800 meshes at 10000rpm, 2g of vermiculite powder is taken and soaked in 30ml of 30% cobalt chloride solution, the reaction is carried out for 24h at 2000rpm, the reaction temperature is 40 ℃, the reaction is carried out for 3 times by washing with deionized water, and the drying treatment is carried out for 24h at 120 ℃.
And (3) uniformly mixing cobalt modified vermiculite powder and 1.5g dicyandiamide in an ultrasonic boiling way, putting the mixture into a high-temperature tubular furnace reactor, introducing inert gas, heating to 800 ℃ at a heating rate of 5 ℃/min, and reacting for 2 hours to obtain the vermiculite carbon nanotube composite material.
Putting the vermiculite carbon nano tube composite material into a hydrothermal kettle, firstly adding 0.001mol/L boric acid and sodium pyrophosphate, stirring for 15min, then adding 0.0001mol/L maleic acid, uniformly stirring the mixture of the vermiculite carbon nano tube composite material, the boric acid, the sodium pyrophosphate and the maleic acid according to the volume ratio of 1:20, dropwise adding 10ml of 0.001mol/L stannous chloride, adding 1.2g of urea after the dropwise adding, setting the temperature to be 110 ℃, crystallizing for 24h, washing with deionized water for 3 times, and drying at the temperature of 60 ℃ for 24h to obtain the vermiculite composite flame retardant material.
Dispersing a vermiculite composite flame retardant material in 100ml of absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite composite flame retardant material to the absolute ethyl alcohol solution is 1:10, uniformly stirring, ultrasonically assisted centrifugally washing for 5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging at 1000rpm for 10min for separation, and drying at 60 ℃ for 24h to obtain the mixture of the vermiculite flame retardant material and the organic plastic material.
Mixing vermiculite flame retardant material and PVC plastic material, adding DOP, wherein the mass ratio of the mixture of the vermiculite flame retardant material and the PVC plastic material to the curing agent is 1:1, performing heat treatment and molding at 200 ℃ to obtain the vermiculite compound flame retardant material with high flame retardant property. The limiting oxygen index LOI is up to 35.4%.
Example 4:
calcining raw ore vermiculite at 900 ℃ to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after washing flotation; the prepared expanded vermiculite is sheared and crushed for 10min to 750 meshes at 10000rpm, 2g of vermiculite powder is taken and soaked in 30ml of 30% nickel chloride solution, the reaction is carried out for 24h at 3000rpm, the reaction temperature is 40 ℃, the deionized water is used for washing 3 times after the reaction, and the drying treatment is carried out for 16h at 110 ℃.
And (3) uniformly mixing nickel modified vermiculite powder and 1.5g of melamine in an ultrasonic boiling way, putting the mixture into a high-temperature tubular furnace reactor, introducing inert gas, heating to 700 ℃ at a heating rate of 5 ℃/min, and reacting for 2 hours to obtain the vermiculite carbon nanotube composite material.
Putting the vermiculite carbon nano tube composite material into a hydrothermal kettle, firstly adding 0.001mol/L boric acid and sodium pyrophosphate, stirring for 15min, then adding 0.0001mol/L DOPO, wherein the volume ratio of the vermiculite carbon nano tube composite material to the mixed liquid of boric acid, sodium pyrophosphate and DOPO is 1:10, stirring uniformly, dropwise adding 20ml of 0.001mol/L stannous chloride, adding 1.2g of urea after the dropwise adding, setting the temperature to 110 ℃, crystallizing for 24h, washing with deionized water for 3 times, and drying at the temperature of 60 ℃ for 24h to obtain the vermiculite composite flame retardant material.
Dispersing a vermiculite composite flame retardant material in 100ml of absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite composite flame retardant material to the absolute ethyl alcohol solution is 1:10, uniformly stirring, ultrasonically assisted centrifugally washing for 5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging at 1000rpm for 10min for separation, and drying at 60 ℃ for 24h to obtain the mixture of the vermiculite flame retardant material and the organic plastic material.
Mixing vermiculite flame retardant material and PVC plastic material, adding DOP, wherein the mass ratio of the mixture of the vermiculite flame retardant material and the PVC plastic material to the curing agent is 1:1, performing heat treatment and molding at 190 ℃ to obtain the vermiculite compound flame retardant material with high flame retardant property. The limiting oxygen index LOI is up to 35.4%.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the vermiculite compound flame retardant material comprises vermiculite, carbon nano tubes, boron phosphate and tin hydroxide, and is characterized by comprising the following steps:
s1, preprocessing vermiculite: calcining raw ore vermiculite to prepare expanded vermiculite, and removing impurities in the expanded vermiculite after washing flotation; shearing and crushing the prepared expanded vermiculite to 100-10000 meshes by a crusher, soaking vermiculite powder in 20% -30% ferric chloride solution, performing iron modification for 1-56h at the rotating speed of 100-20000rpm, wherein the volume ratio of the vermiculite to the ferric chloride solution is 1:5-15, washing and drying at the modification reaction temperature of 25-100 ℃, and standing the treated modified vermiculite powder;
s2, preparing a vermiculite carbon nano tube composite material: uniformly mixing the modified vermiculite powder obtained in the step S1 with a carbon source by ultrasonic boiling, putting the mixture into a high-temperature tube furnace reactor, introducing inert gas, reacting at the temperature of 600-1000 ℃ at the heating rate of 1-20 ℃/min, and obtaining a non-agglomerated vermiculite/carbon nano tube composite material by reaction; the carbon source comprises melamine, pyridine, pyrrole and dicyandiamide;
s3, preparing a vermiculite flame retardant material: putting the vermiculite/carbon nano tube composite material obtained in the step S2 into a hydrothermal kettle, firstly adding 0.0001-0.1mol/L boric acid and sodium pyrophosphate, stirring for 5-100min, then adding 0.0001-0.01mol/L sulfanilic acid, wherein the volume ratio of the vermiculite/carbon nano tube composite material to the mixed liquid of the boric acid, the sodium pyrophosphate and the sulfanilic acid is 1:20-40, stirring uniformly, dropwise adding 1-30ml of 0.0001-0.01mol/L stannous chloride, adding 0.01-10.0g urea after the dropwise adding, crystallizing at the temperature of 80-200 ℃ for 1-48h, washing and drying to obtain the vermiculite compound flame retardant material for later use;
s4, mixing organic plastic materials: dispersing the vermiculite compound flame retardant material obtained in the step S3 in an absolute ethyl alcohol solution, wherein the volume ratio of the vermiculite compound flame retardant material to the absolute ethyl alcohol solution is 1:5-15, uniformly stirring, ultrasonically assisted centrifugally washing for 3-5 times, adding absolute ethyl alcohol, stirring, ultrasonically assisted dispersing, mixing with an organic plastic material, stirring, ultrasonically assisted dispersing to obtain a uniform suspension, centrifuging, and drying to obtain a mixture of the vermiculite compound flame retardant material and the organic plastic material; the organic plastic material comprises ethylene oxide, propylene oxide, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol and polyurethane;
s5, preparing a finished product vermiculite compound flame retardant material: and (3) adding a curing agent into the mixture of the vermiculite flame retardant material and the organic plastic material obtained in the step (S4), and performing heat treatment and molding to obtain the plastic product with high flame retardant property.
2. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the ferric chloride solution in the step S1 is replaced by a cobalt chloride solution or a nickel chloride solution.
3. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the calcining temperature in the step S1 is 550-900 ℃ and the calcining time is 1-100min; the shearing and crushing time of the crusher is 1-200min, the rotating speed is 1000-20000rpm, the reaction time is 1-48h, the drying temperature is 40-180 ℃ and the drying time is 0.5-24h.
4. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the sulfanilic acid in the step S3 is replaced by amino acid, DOPO or maleic acid.
5. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the step S4 is carried out by mixing with the organic plastic material and stirring for 1-55min at 500-1800 rpm.
6. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the mass ratio of the mixture of the vermiculite flame retardant material and the organic plastic material to the curing agent in the step S5 is 2-5:5.
7. the method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the heat treatment molding condition in the step S5 is that the set temperature is 100-300 ℃, and the treatment time is 1-100min.
8. The method for preparing the vermiculite compound flame retardant material according to claim 1, wherein the curing agent in the step S5 comprises ethylene oxide, propylene oxide, glycerol and dioctyl phthalate.
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| CN101503553A (en) * | 2009-02-25 | 2009-08-12 | 西北师范大学 | Vermiculite compositional flame-retardant high-impact polystyrene composite material |
| CN103773253A (en) * | 2014-01-17 | 2014-05-07 | 中南林业科技大学 | Flame-retardant waterproof silicate wood adhesive and preparation method thereof |
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| WO2016206243A1 (en) * | 2015-06-24 | 2016-12-29 | 中国科学院过程工程研究所 | Arc-resistant silicon rubber composite material, preparation method, and uses thereof |
| CN107189427A (en) * | 2017-06-24 | 2017-09-22 | 镇江严彦气体有限公司 | A kind of flame retardant compositions |
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| US9745449B2 (en) * | 2013-07-24 | 2017-08-29 | Lanxess Solutions Us Inc. | Phosphorus containing flame retardants |
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| CN103773253A (en) * | 2014-01-17 | 2014-05-07 | 中南林业科技大学 | Flame-retardant waterproof silicate wood adhesive and preparation method thereof |
| CN104072805A (en) * | 2014-07-02 | 2014-10-01 | 新疆奥吉立节能科技股份有限公司 | Vermiculite-based composite flame retardant and preparation method thereof |
| WO2016206243A1 (en) * | 2015-06-24 | 2016-12-29 | 中国科学院过程工程研究所 | Arc-resistant silicon rubber composite material, preparation method, and uses thereof |
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