CN106032434B - Powder rubber and vulcanized powder rubber and preparation method thereof - Google Patents
Powder rubber and vulcanized powder rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a powdered rubber and a preparation method thereof, and a vulcanized powdered rubber and a preparation method thereof, wherein the powdered rubber contains base rubber and a flame retardant, and the content of the flame retardant is 10-150 parts by weight relative to 100 parts by weight of the base rubber; the vulcanized powder rubber is prepared by vulcanizing the powder rubber, wherein the vulcanization conditions comprise: the temperature of the vulcanization is 120-170 ℃, and the time of the vulcanization is 10-50 minutes. The powder rubber and vulcanized powder rubber provided and prepared by the invention have small particle size and uniform distribution, and simultaneously have flame retardant and toughening properties, and the preparation method is simple.
Description
Technical Field
The present invention relates to a powdered rubber and a vulcanized powdered rubber, a method for producing the same, and a powdered rubber and a vulcanized powdered rubber produced by the method.
Background
With the rapid development of science and technology, plastics, rubbers and fibers have become widely used high molecular materials, but most of the high molecular materials are flammable. In 2010-2013, 386 people are killed in the fire in China and 1967 people are injured, so that 52 billion yuan of direct property loss and higher indirect economic loss are caused, and one of the main reasons for causing the fire is that the high polymer material is inflammable. Therefore, the flame retardant property of the high polymer material and the product thereof is of great significance.
When the rubber polymer containing halogen-carbon bonds is heated to a certain temperature, firstly, dehydrohalogenation (HF and HCl) is decomposed, combustible hydrocarbon is also decomposed, but hydrogen halide is a non-combustible substance and has the flame retardant effect of isolating oxygen and diluting the concentration of the combustible substance. Therefore, the material is difficult to burn and self-extinguishable, and is an inherent flame retardant material, such as fluororubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene and the like.
The silicon rubber takes hydroxyl-terminated polydimethylsiloxane as a basic polymer, and silica chain links in a molecular chain of the silicon rubber can promote materials to form carbon at high temperature when being combusted, so that an antioxidant protective layer is formed, a certain flame retardant effect is achieved, and a large amount of smoke dust and harmful gases cannot be generated.
The powdered rubber has the advantages of convenient metering, contribution to realizing automation and continuity of processing, shortening of mixing time, prolongation of scorching time and the like, and is deeply valued by the rubber industry field. In the later 20 th century, powdered rubber is widely applied to the fields of rubber products, adhesives and polymer modification, and various preparation methods based on a powder forming technology and an isolation technology are formed by taking block rubber (crude rubber blocks and vulcanizing agents), latex, glue solution and suspension as base materials, wherein a spray drying method is a main method for forming powder from the latex and the glue solution, and the prepared powdered rubber is fine and round in particle. CN1330097A discloses a fully vulcanized powder silicone rubber and a preparation method thereof, the method selects low molecular weight organosilicon polymer or copolymer emulsion as raw material, fixes the particle size of silicone rubber particles through irradiation crosslinking, and then dries the silicone rubber particles through a spray drying method to obtain the fully vulcanized powder silicone rubber with the particle size less than or equal to 1 μm, but the powder silicone rubber only has toughening effect and has no good flame retardant property.
Therefore, the powder rubber needs to be prepared by selecting a proper rubber seed, so that the powder rubber has the flame retardant and toughening properties.
Disclosure of Invention
The invention aims to overcome the defect of poor flame retardant property of the conventional powder rubber material, and provides powder rubber and a preparation method thereof.
The inventors of the present invention have found through extensive studies that not only can the obtained powder rubber have flame retardant properties by adding a flame retardant in the preparation process of the powder rubber, but also a powder rubber in a desired particle size range (e.g., an average particle size of 100-200 nm) can be obtained by controlling the amount of the flame retardant. The theory thereof is presumed as: the flame retardant dispersed in the organic solvent functions as a hard template, separates latex particles formed by dissolving the base rubber, obtains different particle size distributions, and then uses a spray drying method without adding a separant to obtain the powder rubber with the particle size of less than 200 nm.
The invention provides a powdered rubber which comprises a base rubber and a flame retardant, wherein the content of the flame retardant is 10-150 parts by weight relative to 100 parts by weight of the base rubber.
The invention also provides a preparation method of the powdered rubber, which is characterized by comprising the following steps: the base rubber is dissolved in an organic solvent and contacted with the flame retardant under stirring, and then the mixture resulting from the contact is spray-dried.
The invention also provides the powder rubber prepared by the method, and the particle size of the powder rubber is 50-700nm, preferably 100-200 nm.
The invention also provides vulcanized powder rubber which is prepared by vulcanizing the powder rubber provided by the invention, wherein the vulcanization conditions comprise that: the temperature of the vulcanization is 120-170 ℃, and the time of the vulcanization is 10-50 minutes.
The powder rubber and vulcanized powder rubber provided by the invention and the preparation method thereof have the advantages that:
1) the powder rubber and vulcanized powder rubber provided and prepared by the invention have flame retardant and toughening properties;
2) the powder rubber and vulcanized powder rubber provided and prepared by the invention have small particle size and uniform distribution;
3) the preparation process is simple;
4) the powder rubber and vulcanized powder rubber provided and prepared by the invention are non-toxic and halogen-free, and are environment-friendly flame retardant toughening agents.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The first aspect of the present invention provides a powdered rubber comprising a base rubber and a flame retardant. The content of the flame retardant may be 10 to 150 parts by weight with respect to 100 parts by weight of the base rubber, and preferably 20 to 100 parts by weight with respect to 100 parts by weight of the base rubber, from the viewpoint of achieving both sufficient flame retardancy and a desired particle diameter. The inventors of the present invention found in experiments that when the content of the flame retardant is 10 to 150 parts by weight relative to 100 parts by weight of the base rubber, the particle diameter of the resulting powder rubber is generally 50 to 700 nm; when the content of the flame retardant is 20 to 100 parts by weight relative to 100 parts by weight of the base rubber, the particle diameter of the resulting powder rubber is usually 100-200 nm.
The particle size of the powder rubber according to the first aspect of the present invention may be 50 to 700nm, preferably 100 to 200 nm. In the present invention, the particle diameter of the powdery rubber is detected by laser dynamic light scattering or a projection electron microscope.
The powder rubber according to the first aspect of the present invention may be a base rubber conventionally used in the art for preparing powder rubber, preferably a base rubber having flame retardant properties by itself, more preferably one or more of silicone rubber, fluororubber and halogenated butyl rubber, and further preferably silicone rubber. Preferably, the silicone rubber is one or more of dimethyl silicone rubber, methyl vinyl phenyl silicone rubber, methyl vinyl trifluoropropyl silicone rubber, phenylene silicone rubber, nitrile silicone rubber and silicon boron rubber, more preferably methyl vinyl silicone rubber. Preferably, the halogenated butyl rubber is neoprene.
According to the powdery rubber of the first aspect of the present invention, the flame retardant may be one or more of a halogen-based flame retardant, a nitrogen-based flame retardant, a phosphorus-nitrogen-based flame retardant, an antimony-based flame retardant, an inorganic phosphorus-based flame retardant, a halogen-phosphorus-based flame retardant, an aluminum-magnesium-based flame retardant, a silicon-based flame retardant, a boron-based flame retardant and a molybdenum-based flame retardant, and preferably is Al (OH)3And/or Mg (OH)2. The inventor of the invention finds that Al (OH) is selected in the test process3And/or Mg (OH)2As the flame retardant, a powdery rubber having a smaller particle diameter and a more uniform particle diameter distribution can be obtained, and the principle thereof is presumed to be: hydroxyl on the surface of the flame retardant dispersed in the solvent forms intermolecular hydrogen bonds with hydrophilic ends on the surface of the micelle, the micelle continuously absorbs monomer droplets dispersed in the solvent to form latex particles, at the moment, the size of the latex particles is limited by the hard template action of the flame retardant, and then the combination probability of the flame retardant and the hydrophilic ends on the surface of the micelle is increased by controlling the dosage of the flame retardant, so that the latex particles present certain particle size distribution.
The powder rubber according to the first aspect of the invention further contains a vulcanizing agent in an amount of 1 to 3 parts by weight based on 100 parts by weight of the base rubber. The vulcanizing agent can be organic peroxide, preferably, the vulcanizing agent is one or more of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, and further preferably, the vulcanizing agent is dicumyl peroxide.
The second aspect of the present invention provides a method for preparing a powdered rubber, comprising: the base rubber is dissolved in an organic solvent and contacted with the flame retardant under stirring, and then the mixture resulting from the contact is spray-dried.
According to the production method of the second aspect of the invention, for the purpose of the invention, the flame retardant may be used in an amount of 10 to 150 parts by weight, preferably 20 to 100 parts by weight, relative to 100 parts by weight of the base rubber.
According to the production method of the second aspect of the present invention, the amount of the organic solvent is not particularly limited, and the base rubber may be dissolved, and preferably, the amount of the organic solvent may be 10 to 100ml per 1g of the base rubber. The dissolution refers to a state in which the base rubber can be brought into a state of being sufficiently dispersed in an organic solvent as a mobile phase without a solid phase visible to the naked eye.
According to the production method of the second aspect of the present invention, the stirring conditions are not particularly limited, and the object of the present invention can be achieved, and the stirring can be performed at room temperature from the viewpoint of energy saving.
According to the production method of the second aspect of the present invention, the stirring time for dissolving the base rubber in the organic solvent is not particularly limited, and the base rubber may be dissolved, and is preferably 20 to 28 hours; the time for bringing the base rubber dissolved in the organic solvent into contact with the flame retardant is not particularly limited, and the base rubber and the flame retardant may be mixed uniformly, and is preferably 1 to 15 hours, more preferably 2 to 8 hours.
According to the preparation method of the second aspect of the present invention, the spray drying may adopt spray drying equipment and conditions which are conventional in the art, and preferably, the inlet temperature of the spray drying equipment may be controlled to be 100 ℃ and 180 ℃ and the outlet temperature may be controlled to be 20-80 ℃.
According to the preparation method of the second aspect of the present invention, the organic solvent may be an organic solvent conventionally used in the art for preparing powdered rubber, preferably one or more of toluene, trichloroethylene and methyl ethyl ketone, more preferably toluene.
According to the production method of the second aspect of the invention, in order to obtain a powder rubber of a smaller particle diameter and improve safety and drying efficiency at the time of spray drying, a mixed solution of the base rubber and the organic solvent may be diluted with a diluent, preferably water, after the base rubber is dissolved in the organic solvent and before being brought into contact with the flame retardant. The amount of the water to be used is not particularly limited, and preferably, the volume ratio of the water to the organic solvent is from 0.5 to 10: 1, more preferably 1 to 8: 1. the time for stirring and contacting the mixed solution of the base rubber and the organic solvent with water is not particularly limited, and the mixed solution of the base rubber and the organic solvent may be mixed with water uniformly, and is preferably 0.5 to 5 hours, and more preferably 1 to 3 hours.
The preparation method according to the second aspect of the present invention further comprises: the contacting is carried out in the presence of a vulcanizing agent in an amount which is conventional in the art for the vulcanizing agent added in the preparation of rubber, preferably in an amount of 1 to 3 parts by weight relative to 100 parts by weight of the base rubber.
According to the preparation method of the second aspect of the present invention, the adding order of the vulcanizing agent and the flame retardant is not particularly limited, and the vulcanizing agent and the flame retardant may be added simultaneously or sequentially.
The base rubber, flame retardant and vulcanizing agent of the second aspect of the present invention are the same as those of the first aspect of the present invention, and are not described herein again.
The invention also provides a powder rubber prepared by the method according to the second aspect of the invention, wherein the particle size of the powder rubber is 50-700nm, preferably 100-200 nm.
In a third aspect, the present invention provides a vulcanized powder rubber obtained by vulcanizing the powder rubber provided by the present invention, wherein the vulcanization conditions include: the temperature of the vulcanization is 120-170 ℃, and the time of the vulcanization is 10-50 minutes.
According to the vulcanized powder rubber of the third aspect of the present invention, when a vulcanizing agent is contained in the powder rubber, the powder rubber is directly vulcanized to obtain a vulcanized powder rubber; when the powder rubber does not contain a vulcanizing agent, 1 to 3 parts by weight of the vulcanizing agent is firstly contacted with about 100 parts by weight of the powder rubber, and then vulcanized to obtain vulcanized powder rubber.
The vulcanized powder rubber according to the third aspect of the present invention has a particle size of 50 to 700nm, preferably 100 to 200 nm.
The powder rubber and vulcanized powder rubber of the present invention can be used in a manner conventional in the art, for example, as an additive in the production of products, preferably as a modifier for polymers such as polycarbonate, polyvinyl chloride (PVC), phenolic resins, and epoxy resins, to increase the toughness and reduce flammability of the polymers.
The following examples will help illustrate the invention without limiting its scope.
The particle size of the powdered rubber is detected by a laser dynamic light scattering electron microscope.
The reagents used in the following examples are all commercially available without specific reference.
Examples 1 to 4 are intended to illustrate the powder rubber and vulcanized powder rubber provided by the present invention and the preparation method thereof.
Example 1
100g of methyl vinyl phenyl silicone rubber (Shanghai resin factory Co., Ltd., brand: 120) was placed in a vessel, 1L of trichloroethylene was added thereto, stirred for 28 hours, then 8L of water was added thereto, stirred for 2 hours, and then while stirring, 1g of a vulcanizing agent, di-tert-butyl peroxide, and 150g of a flame retardant, Mg (OH) were added thereto in this order2And stirring for 2 hours to achieve uniform mixing to obtain the polymer latex. The polymer latex was spray-dried at an inlet temperature of 100 ℃ and an outlet temperature of 20 ℃ in a spray-drying apparatus, and then the powdered rubber obtained after drying was collected in a cyclone, and the average particle size of the obtained powdered rubber was about 450 nm.
And (3) putting the powder rubber obtained after spray drying into a thermal oxidation aging oven with the temperature of 120 ℃ for vulcanization for 20min to obtain vulcanized powder rubber, wherein the average particle size of the vulcanized powder rubber is about 450 nm.
Example 2
100g of dimethyl silicone rubber (Zhonghao Chenguang chemical research institute Co., Ltd., trade name: 101) was placed in a vessel, 4L of methyl ethyl ketone was added thereto, stirred for 20 hours, 12L of water was added thereto, stirred for 2 hours, and then, while stirring, 2g of t-butyl perbenzoate as a vulcanizing agent and 100g of a flame retardant Al (OH) were sequentially added3And stirring for 6 hours to obtain uniform mixing, thereby obtaining the polymer latex. And (2) spray-drying the polymer latex, controlling the inlet temperature of spray-drying equipment to be 180 ℃ and the outlet temperature to be 80 ℃, and then collecting the dried powder silicon rubber in a cyclone separator, wherein the average particle size of the obtained powder rubber is about 200 nm.
And (3) placing the powder rubber obtained after spray drying in a thermal oxidation aging oven at the temperature of 170 ℃ for vulcanization for 40min to obtain vulcanized powder rubber, wherein the average particle size of the vulcanized powder rubber is about 200 nm.
Example 3
100g of methyl vinyl silicone rubber (Shanghai resin factory Co., Ltd., brand: 120) was placed in a vessel, 4L of toluene was added thereto, stirred for 24 hours, 6L of water was added thereto, stirred for 3 hours, and then, while stirring, 2g of dicumyl peroxide (DCP), a vulcanizing agent, 80g of a flame retardant Al (OH), were sequentially added3And stirring is continued for 8 hours to achieve uniform mixing, so as to obtain the polymer latex. Spray-drying the polymer latex, controlling the inlet temperature of spray-drying equipment at 140 ℃ and the outlet temperature at 50 ℃, and collecting the dried powder silicon rubber in a cyclone separator, wherein the average particle size of the obtained powder rubber is about 150 nm.
And (3) placing the obtained powder rubber after spray drying in a thermal oxidation aging box at the temperature of 150 ℃ for vulcanizing for 30min to obtain vulcanized powder rubber, wherein the average particle size of the vulcanized powder rubber is about 150 nm.
Example 4
100g of chloroprene rubber (available from Nippon Denshoku Kogyo Co., Ltd.; trade name: PM40-NS) was charged into a vessel, 10L of toluene was added thereto, the mixture was stirred for 18 hours, 10L of water was further added thereto, the mixture was stirred for 0.5 hour, and then, while stirring, 3g of DCP as a vulcanizing agent and 10g of Al (OH) as a flame retardant were added thereto3And stirring is continued for 12 hours to achieve uniform mixing, so as to obtain the polymer latex. And (2) spray-drying the polymer latex, controlling the inlet temperature of spray-drying equipment to be 190 ℃ and the outlet temperature to be 90 ℃, and then collecting the dried powder silicon rubber in a cyclone separator, wherein the average particle size of the obtained powder rubber is 400 nm.
And (3) putting the powder rubber obtained after spray drying into a thermal oxidation aging box with the temperature of 110 ℃, and vulcanizing for 50min to obtain vulcanized powder rubber, wherein the average particle size of the vulcanized powder rubber is about 400 nm.
Comparative example 1
Powdered rubber and vulcanized powdered rubber were prepared as described in example 1 of CN 1330097A. The average particle diameter of the obtained powdered rubber was about 200nm, and the average particle diameter of the obtained vulcanized powdered rubber was about 200 nm.
The powder rubbers and vulcanized powder rubbers prepared in examples 1 to 4 and comparative example 1 were tested for their notched impact strength (J/m)-1) And UL94 flame rating, wherein notched impact strength (J/m)-1) And UL94 flame rating, respectively, for toughening and flame retardant properties, the results are shown in Table 1.
The notch impact strength is 172.6J/m-1UL94 polycarbonate with combustion grade V-2, pre-mixing powder rubber or vulcanized powder rubber with the polycarbonate at the weight ratio of 40:100 at room temperature, and then melt-extruding and granulating by a double-screw extruder; the extrusion temperature is 240-260 ℃, the neck ring temperature is 250 ℃, and the screw rotating speed is 200 r/min. Drying the extruded granules, performing injection molding by using an injection molding machine to obtain a standard test sample strip for vertical combustion and notch impact test, and then testing the notch impact strength and UL94 combustion grade of the composite material, wherein the specific steps are as follows:
1) notched impact strength: according to the standard ASTM D256, adopting a ZBC1151 type impact tester of the Meister Industrial Co Ltd to carry out toughening performance test, wherein the larger the notch impact strength is, the better the toughening performance of the composite material is;
2) UL94 flame rating: according to the standard ASTM D3801/UL94, the flame retardant property of the composite material is gradually deteriorated with the flame retardant grades V-0, V-1, V-2 and HB by adopting a CZF type horizontal vertical combustion tester to test and analyze the flame retardant property of the composite material.
TABLE 1
As can be seen from the comparison of the examples and the comparative examples, the powder rubber and vulcanized powder rubber prepared by the method provided by the invention have better toughening property and flame retardant property.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (9)
1. A powder rubber comprises a base rubber and a flame retardant, wherein the content of the flame retardant is 20-100 parts by weight relative to 100 parts by weight of the base rubber, and the particle size of the powder rubber is 100-200 nm; the flame retardant is Al (OH)3And/or Mg (OH)2；
The powder rubber is prepared by the following method: dissolving base rubber into an organic solvent under the condition of stirring, contacting with a flame retardant, and then spray-drying a mixture obtained by contacting; after the base rubber is dissolved in the organic solvent, before the base rubber is contacted with the flame retardant, diluting the mixed solution of the base rubber and the organic solvent by using water, wherein the volume ratio of the water to the organic solvent is 0.5-10: 1;
the powder rubber also contains a vulcanizing agent, wherein the vulcanizing agent accounts for 1-3 parts by weight based on 100 parts by weight of the base rubber, and the vulcanizing agent is one or more of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxide hexane;
the base rubber is silicon rubber.
2. The powder rubber according to claim 1, wherein the silicone rubber is selected from one or more of dimethyl silicone rubber, methyl vinyl phenyl silicone rubber, methyl vinyl trifluoropropyl silicone rubber, phenylene silicone rubber, nitrile silicone rubber, and silicon boron rubber.
3. The powder rubber according to claim 1, wherein the vulcanizing agent is dicumyl peroxide.
4. A method for preparing the powdered rubber according to any one of claims 1 to 3, comprising: dissolving a base rubber into an organic solvent under stirring and contacting with a flame retardant, and then spray-drying a mixture obtained by the contact, the amount of the flame retardant being 20 to 100 parts by weight relative to 100 parts by weight of the base rubber; the flame retardant is Al (OH)3And/or Mg (OH)2(ii) a After the base rubber is dissolved in the organic solvent, before the base rubber is contacted with the flame retardant, diluting the mixed solution of the base rubber and the organic solvent by using water, wherein the volume ratio of the water to the organic solvent is 0.5-10: 1; said contacting is carried out in the presence of a vulcanizing agent in an amount of 1 to 3 parts by weight per 100 parts by weight of the base rubber; the vulcanizing agent and the flame retardant are added in sequence.
5. The method of claim 4, wherein the organic solvent is one or more of toluene, trichloroethylene and methyl ethyl ketone.
6. The method of claim 5, wherein the organic solvent is toluene.
7. A vulcanized powder rubber obtained by vulcanizing the powder rubber according to any one of claims 1 to 3 under conditions comprising: the temperature of the vulcanization is 120-170 ℃, and the time of the vulcanization is 10-50 minutes.
8. The vulcanized powder rubber according to claim 7, wherein the vulcanized powder rubber has a particle size of 50 to 700 nm.
9. The vulcanized powder rubber as set forth in claim 8, wherein the particle size of the vulcanized powder rubber is 100-200 nm.
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| CN109467934A (en) * | 2018-10-29 | 2019-03-15 | 江苏宏鹏电气科技有限公司 | A kind of anti-aging cable insulation layer formula of high temperature resistant |
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| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| CN101182376A (en) * | 1998-12-18 | 2008-05-21 | Pku粉末橡胶联合有限公司 | Process for making compounded rubber powders |
| CN101724187A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Rubber composition and preparation method thereof |
| CN102453265A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Modified powdered rubber and preparation method thereof |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method for flame-retardant powdered rubber |
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| JPH05230289A (en) * | 1992-02-19 | 1993-09-07 | Bridgestone Corp | Flame-retardant rubber composition |
| CN1155652C (en) * | 2000-11-03 | 2004-06-30 | 中国石油化工股份有限公司 | Toughened plastics and its preparing process |
| NO328601B1 (en) * | 2002-06-07 | 2010-03-29 | Elkem As | Elastomeric compositions, process for the preparation of elastomeric compositions and the use of microsilica as a modifier in elastomeric compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101182376A (en) * | 1998-12-18 | 2008-05-21 | Pku粉末橡胶联合有限公司 | Process for making compounded rubber powders |
| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| CN101724187A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Rubber composition and preparation method thereof |
| CN102453265A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Modified powdered rubber and preparation method thereof |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method for flame-retardant powdered rubber |
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