CN101280075B - Flame-retardant styrene-butadiene rubber - Google Patents
Flame-retardant styrene-butadiene rubber Download PDFInfo
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- CN101280075B CN101280075B CN2008100182466A CN200810018246A CN101280075B CN 101280075 B CN101280075 B CN 101280075B CN 2008100182466 A CN2008100182466 A CN 2008100182466A CN 200810018246 A CN200810018246 A CN 200810018246A CN 101280075 B CN101280075 B CN 101280075B
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Abstract
The invention provides a flame-retardant styrene-butadiene rubber, which is formed by styrene-butadiene rubber and flame retardant through mechanical mixing and internal mixing; wherein, the flame retardant is nano-loess powders, or can be a composite flame retardant prepared by nano-loess powders and aluminum hydroxide or/and nano-magnesium hydroxide. The flame retardants of the invention are nano-powders, which can be evenly dispersed in styrene-butadiene rubber matrix in the mixing process with styrene-butadiene rubber; therefore, the flame retardants have excellent physical properties. The flame-retardant styrene-butadiene rubber of the invention has low cost, environmental friendly performance and good fire-retardant effect. Based on measurement, the oxygen index of the flame-retardant styrene-butadiene rubber is more than 28, or even up to 36; the combustion performance is in UL94 V-1 to UL94 V-0 level.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of styrene-butadiene rubber, relate in particular to a kind of flame-retardant styrene-butadiene rubber.
Background technology
The rubber technology of 21 century will develop towards high performance and functionalization direction.Along with continuing to bring out of nano material and updating of rubber nano enhancing theory and technology, rubber nano composite material has obtained flourish.The compound physicals and the functional performance that can improve polymer materials of nano-powder and polymkeric substance, particularly when nano-powder has some specific functions owing to self chemical structure and physical property, for high viscosity state processing, the significant elastomeric material of nanometer reinforcing effect, potentiality are very big.
Styrene-butadiene rubber(SBR) is by divinyl and styrene copolymerized and elastomerics that obtain.The outward appearance of styrene-butadiene rubber(SBR) is light tan, little band vinylbenzene smell.Its linear macromolecule one-piece construction is amorphous, and crystallization tendency is arranged unlike natural rubber.Contain two keys in its macromolecular chain segment, can use sulfur cross-linking.Main as making various tires, sebific duct, rubber overshoes and other multiple rubber items.But because styrene-butadiene rubber(SBR) is inflammable in air, its application has been subjected to restriction to a great extent.
Aluminium hydroxide is the maximum and most widely used inorganic fire-retarded additive of consumption.Aluminium hydroxide can not only be fire-retardant as fire retardant, prevents to be fuming, do not produce dropping, do not produce toxic gas, and in rubber, be uniformly dispersed, good processability has good fire retardation, especially can satisfy the requirement of the halogen-free flameproof of domestic electric wire, cable.Therefore, obtain to use more widely, usage quantity is also increasing year by year.Use range: industries such as thermosetting resin, thermoplastics, synthetic rubber, coating and building materials.
Magnesium hydroxide decomposes between 340 ℃～490 ℃, and Heat stability is good has good fire-retardant and smoke effect, is suitable for the higher polyolefin plastics of processing temperature especially.The compound use of aluminium hydroxide and magnesium hydroxide can replenish mutually, and its flame retardant properties is better than independent result of use.
Loess, physical properties show as loose, porous crack, very easily infiltration.In conjunction with not tight, porosity is generally 40%～50% between the loess particle.Typical loess is yellow-gray or brown xanchromatic dust and silty sand particulate composition not, the quality homogeneous.The mineralogical composition of loess has detrital mineral, clay mineral and authigenic mineral 3 classes.Detrital mineral mainly is quartz, feldspar and mica, accounts for 80% of detrital mineral, and next has pyroxene, hornblende, pistacite, chlorite, magnetite etc.; In addition, carbonate minerals content is more in the loess, mainly is calcite.Clay mineral mainly is illite, montmorillonite, kaolinite, pyrrhosiderite, contains turgite etc.The chemical ingredients of loess is with SiO
2Preponderating, is Al secondly
2O
3, CaO, be Fe once more
2O
3, MgO, K
2O, Na
2O, FeO, TiO
2With MnO etc.The distribution of China's loess is very extensive, and area reaches 540,000 square kilometres, accounts for 60 percent of national land area.Owing to contain abundant ignition-proof element in the loess, and have nontoxic, non-volatile, as to press down cigarette and reduction toxic gas function, can be used as fire retardant.
Because the nano-loess powder has natural nano-lamellar structure, just can peel off into the lamella of nanoscale by simple compounding technology, be dispersed in the polymeric matrix, make polymer based nanocomposites; Only need filler seldom can make matrix material have quite high intensity, Young's modulus, dimensional stability, thermostability and barrier property etc., therefore more and more be subjected to the attention of domestic and international relevant industries.
Summary of the invention
The purpose of this invention is to provide a kind of good flame retardation effect, cost is low, the flame-retardant styrene-butadiene rubber of non-environmental-pollution.
Flame-retardant styrene-butadiene rubber of the present invention, be by styrene-butadiene rubber and fire retardant mixing and, wherein fire retardant adopts the nano-loess powder.
Experimental results demonstrate that the mass ratio of styrene-butadiene rubber(SBR) and nano-loess powder is in 1: 0.1～1: 5 scope the time, and is little to the physicals influence of styrene-butadiene rubber(SBR).
In order further to improve flame retardant properties, the fire retardant that the present invention adopts also can by nano-loess powder and nano-aluminum hydroxide or/and nano-sized magnesium hydroxide is composite must composite flame-retardant agent.To be nano-loess powder and magnesium hydroxide or styrene-butadiene rubber(SBR) carry out composite with 1: 0.1～1: 10 mass ratio its proportioning ratio; Or nano-loess powder and magnesium hydroxide, aluminium hydroxide carry out composite with 1: 0.1: 0.1～1: 10: 10 mass ratio.Aluminium hydroxide, magnesium hydroxide not only can play fire retardation, and can play filling effect.They have thermally-stabilised good, efficient, press down cigarette, resistance drip, fill safety, to characteristics such as environment are pollution-free substantially, the two is composite, can bring into play the cooperative flame retardant effect of these two kinds of inorganic components, widen effective resistance combustion temperature scope, and significantly improve the flame retarding efficiency of composite inorganic fire retardant.
Styrene-butadiene rubber(SBR), nano-loess powder, nano-aluminum hydroxide, nano-sized magnesium hydroxide that the present invention adopts all can be bought on market.Wherein the granularity of nano-loess powder is 20～50nm, is produced by Shanghai Huzheng Nano-Tech Co., Ltd.; The granularity of nano-aluminum hydroxide, nano-sized magnesium hydroxide is 20nm, produces by Shenzhen nanometer Gao Ke limited-liability company.
The preparation of flame-retardant styrene-butadiene rubber of the present invention can mix by the machinery ginseng, mixing the forming of mode of banburying.When adopting composite flame-retardant agent, can be earlier with nano-loess powder, magnesium hydroxide or/and aluminium hydroxide mixes in the mode of mechanical blending, form composite flame-retardant agent, carry out styrene-butadiene rubber(SBR) and composite flame-retardant agent mixing again; Also can be with styrene-butadiene rubber(SBR) and nano-loess powder, magnesium hydroxide or/and aluminium hydroxide directly carries out mixing.
The present invention compared with prior art has the following advantages:
1, flame-retardant styrene-butadiene rubber of the present invention is that fire retardant forms with styrene-butadiene rubber(SBR) mixing banburying with nano-loess powder or its compound, has good flame retardancy.The oxygen index of composite flame-proof material of the present invention can reach more than 28 after measured, and combustionproperty is UL94V-1～UL94V-0 level.
2, flame-retardant styrene-butadiene rubber of the present invention, its fire retardant all belongs to nanometer grade powder, in mixing process, can be dispersed in the styrene-butadiene rubber(SBR) matrix, thereby have excellent physicals.
3, loess composite flame-retardant agent of the present invention does not produce toxic gas, environmental protection, pollution-free based on inorganics during burning.
4, the loess composite flame-retardant agent wide material sources that adopt of the present invention are cheap, thereby greatly reduce the cost of fire retardant material, and the suitability for industrialized production of fire retardant material is had huge pushing effect.
5, the preparation of flame-retardant styrene-butadiene rubber of the present invention, be with machinery ginseng mix, banburying forms, production technique is simple, cost is low.
Embodiment
Further specify the preparation and the flame retardant effect of flame retardant type styrene-butadiene rubber(SBR) below by example.
Embodiment 1: nano-loess powder and nano-aluminum hydroxide is even with the mode thorough mixing of mechanical blending by 1: 1 mass ratio, get the loess composite flame-retardant agent; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 3 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 28.2, and combustionproperty is the UL94V-1 level.
Embodiment 2: nano-loess powder and nano-sized magnesium hydroxide is even with the mode thorough mixing of mechanical blending by 1: 1 mass ratio, get the loess composite flame-retardant agent; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 3 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 28.4, and combustionproperty is the UL94V-1 level.
Embodiment 3: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 1: 1 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 2 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 28.9, and combustionproperty is the UL94V-1 level.
Embodiment 4: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 10: 1: 10 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 29.5, and combustionproperty is the UL94V-0 level.
Embodiment 5: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 5: 7: 1 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 2: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 33, and combustionproperty is the UL94V-0 level.
Embodiment 6: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 10: 5 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 3: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 34.5, and combustionproperty is the UL94V-0 level.
Embodiment 7: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 10: 10 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 4: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 36, and combustionproperty is the UL94V-0 level.
Embodiment 8: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 5: 8 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 3: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 34, and combustionproperty is the UL94V-0 level.
Embodiment 9: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 2: 1: 7 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 2: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 31, and combustionproperty is the UL94V-0 level.
Embodiment 10: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 5: 5 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 29.5, and combustionproperty is the UL94V-0 level.
Embodiment 11: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 3: 10: 4 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 2 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 28, and combustionproperty is the UL94V-1 level.
Embodiment 12: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 7: 3 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 1: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 29.2, and combustionproperty is the UL94V-0 level.
Embodiment 13: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 10: 7: 7 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 2: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 28, and combustionproperty is the UL94V-1 level.
Embodiment 14: nano-loess powder, nano-sized magnesium hydroxide and nano-aluminum hydroxide are got the loess composite flame-retardant agent by 1: 6: 6 mass ratio with the mode thorough mixing of mechanical blending; Then that gained loess compound flame retardant and styrene-butadiene rubber(SBR) is mixing with rubber machine with 3: 1 mass ratio, get flame-retardant styrene-butadiene rubber.After measured, its oxygen index can reach 32, and combustionproperty is the UL94V-0 level.
Claims (6)
1. flame-retardant styrene-butadiene rubber is by styrene-butadiene rubber(SBR) and fire retardant is mixing forms; It is characterized in that: described fire retardant is the nano-loess powder, and the mass ratio of styrene-butadiene rubber(SBR) and nano-loess powder is 1: 0.1～1: 5.
2. flame-retardant styrene-butadiene rubber according to claim 1, it is characterized in that: the granularity of described nano-loess powder is 20～50nm.
3. flame-retardant styrene-butadiene rubber as claimed in claim 1 or 2 is characterized in that: described fire retardant be nano-loess powder and nano-aluminum hydroxide or/and nano-sized magnesium hydroxide is composite composite flame-retardant agent.
4. as flame-retardant styrene-butadiene rubber as described in the claim 3, it is characterized in that: described fire retardant is to carry out composite by nano-loess powder and magnesium hydroxide with 1: 0.1～1: 10 mass ratio.
5. as flame-retardant styrene-butadiene rubber as described in the claim 3, it is characterized in that: described fire retardant is to carry out composite by nano-loess powder and aluminium hydroxide with 1: 0.1～1: 10 mass ratio.
6. as flame-retardant styrene-butadiene rubber as described in the claim 3, it is characterized in that: described fire retardant is to carry out composite by nano-loess powder and magnesium hydroxide, aluminium hydroxide with 1: 0.1: 0.1～1: 10: 10 mass ratio.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100182466A CN101280075B (en) | 2008-05-09 | 2008-05-09 | Flame-retardant styrene-butadiene rubber |
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| CN2008100182466A CN101280075B (en) | 2008-05-09 | 2008-05-09 | Flame-retardant styrene-butadiene rubber |
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| CN101280075B true CN101280075B (en) | 2010-11-10 |
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| CN103570856A (en) * | 2012-07-26 | 2014-02-12 | 柳州煜华科技有限公司 | Rubber and preparation method thereof |
| CN104194101B (en) * | 2014-09-22 | 2016-01-06 | 江阴海达橡塑股份有限公司 | A kind of preparation method of halogen-free fireproof rubber |
| CN104558721A (en) * | 2014-12-25 | 2015-04-29 | 安徽泓光网络工程有限公司 | Environment-friendly flame-retardant rubber formula |
| CN104962030A (en) * | 2015-07-12 | 2015-10-07 | 陆思烨 | Natural antibacterial and aging-resistant ABS (acrylonitrile butadiene styrene copolymer) material and preparation method thereof |
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