CN102352057B - Non-halogen composite flame retardant and application thereof in preparation of flame retardant thermoplastic elastomer composite - Google Patents
Non-halogen composite flame retardant and application thereof in preparation of flame retardant thermoplastic elastomer composite Download PDFInfo
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Abstract
The invention provides a non-halogen composite flame retardant with good flame resistance and less influence on the mechanical properties of the thermoplastic elastomer, belonging to the technical field of the composite filler. The non-halogen composite flame retardant is prepared by mixing raw materials, namely palygorskite clay, melamine phosphate and hollow microspheres. As hollow microspheres are added in the composite flame retardant to prepare the flame retardant thermoplastic elastomer composite, the flame resistance of the composite is increased and the composite has good processing flowability.
Description
Technical field
The present invention relates to a kind of Halogenless composite fire retardant, relate in particular to a kind of Halogenless composite fire retardant that forms as raw material is composite take palygorskite clay, melamine phosphate and cenosphere, belong to the compounded mix technical field.The invention still further relates to the application of this Halogenless composite fire retardant in the preparation flame-retardant thermoplastic elastomer.
Background technology
Thermoplastic elastomer has the physical and mechanical properties of vulcanized rubber and the performance of technical process of nonrigid plastic.Owing to not needing to pass through again hot sulfurization as rubber, thereby use simple plastic processing machinery can make at an easy rate the finished product.Its these characteristics make the rubber industry Production Flow Chart shorten l/4, and energy efficient 25% ~ 40% is raised the efficiency 10 ~ 20 times, can be rated as rubber industry material and Technology revolution again.
Thermoplastic elastomer is widely used in making the daily goods such as rubber overshoes, adhesive plaster, various industrial goods and the food medical fields such as waterproof roll, sebific duct, adhesive tape, adhesive tape, offset plate, glue spare, electric wire envelope curve and tackiness agent.Simultaneously, thermoplastic elastomer also can replace rubber to be used in a large number the interchangeable heat plastic resins such as PVC, PE, PP, PS even above the modification of the engineering plastics such as PU, PA, CA, makes plastics industry brand-new situation also occur.
But also there are some shortcomings in thermoplastic elastomer, and wherein inflammableness makes it in use cause very large harm to the security of the lives and property.Combustionproperty to the use material in China's national standard and part industry standard has provided clear and definite regulation, the requirement oxygen index must be greater than 30, the horizontal vertical burning reaches UL94V-0 level or UL94V-1, so must carry out thermoplastic elastomer flame-retardant modifiedly, make it be applied to widely every field.
In recent years, a large amount of researchers have carried out various flame-retardant modified researchs to thermoplastic elastomer, a kind of preparation method of non halogen wire and cable sheath material is for example disclosed in Chinese patent CN101205324A, but it is various that this material preparation process is added fire-retardant raw material type, and only mention flame resistivity and be " success ", fire retardancy is not carried out clear and definite description; Do not investigate in addition the mechanical property of material yet.The people such as the Li Xiaoyan (performance that thermoplastic polyolefin elastomer/primary ammonium phosphate flame retardant composites is, Dalian Polytechnic University's journal, 2010,29 (2): 137-139) studied the fire retardancy of primary ammonium phosphate to thermoplastic elastomer, but oxygen index only has 25.9, can not satisfy country to the requirement of electric wire and building materials.
Summary of the invention
Purpose of the present invention provides a kind of flame retardant properties good for problems of the prior art, does not affect again the Halogenless composite fire retardant of thermoplastic elastomer mechanical property.
Another object of the present invention is to provide the application of a kind of this Halogenless composite fire retardant in the preparation flame-retardant thermoplastic elastomer.
(1) Halogenless composite fire retardant
Halogenless composite fire retardant of the present invention is to be that raw material mixes by palygorskite clay, melamine phosphate and cenosphere.
Polygorskite be a kind of tool chain laminate structure contain Shuifu County's magnesium silicate clay mineral, its density is low, paler colour can not have a strong impact on its weight and the transparency after compound with polymer; Polygorskite hardness easily is processed into the nano-micrometre grade particles 2 ~ 2.5; The microvoid structure of polygorskite, make it to gas, strong adsorption be arranged, the hollow heat insulation thermal insulation can be blocked the transmission of heat, its suction and water retention property, at high temperature can produce water vapour blocking-up oxygen, polygorskite itself is non-volatile, and effect is lasting, cheap, smog is little, having fire-retardant, as to press down cigarette and reduction toxic gas function concurrently, is a kind of desirable nuisanceless fire retardant material.
Melamine phosphate can decompose generation ammonia and hydroxyacid containing phosphorus when being heated, ammonia can dilute the concentration of the gases such as inflammable gas and airborne oxygen, thereby it stops the effect of burning.The oxygen acid (comprising some polymkeric substance in them) that generates is strong dewatering agent, can make the rapid dehydration carbonization of polymkeric substance, and the blocking-up polymkeric substance contacts with oxygen, plays fire retardation in solid phase.In addition, contain the PO radical in the formed gaseous product of organic phosphorus flame retardant thermolysis, it can catch H radical and OH radical, causes H and OH radical concentration in flame greatly to descend, and plays the effect that suppresses the burning chain reaction.
Cenosphere is a kind of Multifunction non-metallic powder material, and diameter is between 0.01-400 μ m, and outward appearance is greyish white or grey, loose, spherical, good fluidity, hollow, hard shell is arranged, cenosphere belongs to manosil AS class inorganic powder material, and major ingredient is SiO
2And Al
2O
3, be described as " Space Age material ".Due to the cenosphere heat-drawn wire greater than 1350 ℃, contained CO in its cavity
2, N
2Be choke damp; Cenosphere can form complete tectum at material surface, and its low-down heat conductivility has intercepted the transmission of heat to inner substrate surface, thereby has reduced the thermal decomposition rate of base material; Lower because the thermoplastic elastomer based material decomposes the speed that discharges combustible gas, cause flame significantly to reduce in the velocity of propagation of material surface.Therefore, cenosphere can improve the flame retardant properties of thermoplastic elastic material.
The present invention mixes palygorskite clay, melamine phosphate and cenosphere composite, makes three's fire retardation cooperatively interact, mutually promotes, thereby further improved the flame retardant properties of composite flame-retardant agent.
Through a large amount of groping and testing, we find that in composite flame-retardant agent, each material component is by following weight part proportioning, and composite flame-retardant agent all has good flame retardant properties:
40 parts of palygorskite clay, 40 ~ 55 parts of melamine phosphates, 20 ~ 5 parts of cenospheres.
Optimum ratio is:
40 parts of palygorskite clay, 43 ~ 52 parts of melamine phosphates, 17 ~ 8 parts of cenospheres.
(2) flame retardant thermoplastic elastomer composite material
Above-mentioned Halogenless composite fire retardant and thermoplastic elastomer mixed melting are extruded; The add-on of fire retardant is 20 ~ 50% of thermoplastic elastic weight.
For resistance of aging and the processing characteristics that improves thermoplastic elastomer, in melting process, also can add some processing aids, as antioxidant, UV light absorber and lubricant etc., the add-on of processing aid can be with reference to the add-on of various processing aids in prior art.
Described coupling agent is γ-r-chloropropyl trimethoxyl silane; γ-chloropropyl triethoxysilane; Gamma-chloropropylmethyldimethoxysilane; γ-chloropropyl methyldiethoxysilane; Two-(the silica-based propyl group of γ-triethoxy) tetrasulfide; The mixture (1:1) of two-(the silica-based propyl group of γ-triethoxy) tetrasulfide and carbon black; The mixture (1:1) of two-(the silica-based propyl group of γ-triethoxy) tetrasulfide and white carbon black; Two-(the silica-based propyl group of γ-triethoxy) tetrasulfide wax; γ-mercaptopropyl trimethoxysilane; Gamma-mercaptopropyltriethoxysilane; γ-aminopropyltrimethoxysilane; γ-aminopropyl triethoxysilane; Titante coupling agent; The zirconate coupling agent; The aluminate coupling agent; Stearic acid, Zinic stearas, calcium stearate, the mixture of one or more in barium stearate.
Described thermoplastic elastomer has: styrene compound (as SBS, SIS, SEBS, SEPS), alkenes compounds (TPO, TPV), double vinyl compound (TPB, TPI), polyvinyl chloride-base compound (TPVC, TCPE), ammonia ester compound (TPU), ester compound (TPEE), amides (TPAE), organic fluorine compounds (TPF) etc.
Owing to having added cenosphere, for the preparation of flame retardant thermoplastic elastomer composite material, not only improve the flame retardant properties of matrix material in composite flame-retardant agent of the present invention, and made matrix material have good processing flowability.
Embodiment
Below by specific embodiment, the preparation of composite flame-retardant agent of the present invention, flame-retardant thermoplastic elastomer and the performance of thermoplastic elastomer are described in detail.
Embodiment 1
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 43 parts of melamine phosphates, 17 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, 45 parts of the Halogenless composite fire retardants of modification are mixed with thermoplastic elastomer TPO100 part, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material TPO.Above-mentioned fire retardant and TPO are in mass parts.
The performance of flame retardant resistance matrix material TPO: oxygen index: 32; Under the nonflame condition, smoke density 280; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 354%.
Embodiment 2
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 48 parts of melamine phosphates, 12 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, then with modification 35 parts of Halogenless composite fire retardants mix with 100 parts of thermoplastic elastomer TPU, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material TPU.Above-mentioned fire retardant and TPU are in mass parts.
The performance of flame retardant resistance matrix material TPU: oxygen index: 36; Under the nonflame condition, smoke density 265; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 820%.
Embodiment 3
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 50 parts of melamine phosphates, 10 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, 50 parts of the Halogenless composite fire retardants of modification are mixed with 100 parts of thermoplastic elastomer TPV, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material TPV.Above-mentioned fire retardant and TPV are in mass parts.
The performance of flame retardant resistance matrix material TPV: oxygen index: 38; Under the nonflame condition, smoke density 244; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 400%.
Embodiment 4
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 40 parts of melamine phosphates, 20 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, 40 parts of the Halogenless composite fire retardants of modification are mixed with 100 parts of thermoplastic elastomer SEBS, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material SEBS.Above-mentioned fire retardant and SEBS are in mass parts.
The performance of flame retardant resistance matrix material SEBS: oxygen index: 32; Under the nonflame condition, smoke density 287; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 360%.
Embodiment 5
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 55 parts of melamine phosphates, 5 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, then 20 parts of the Halogenless composite fire retardants of modification are mixed with 100 parts of thermoplastic elastomer PBT, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material PBT.Above-mentioned fire retardant and PBT are in mass parts.
The performance of flame retardant resistance matrix material PBT: oxygen index: 32; Under the nonflame condition, smoke density 279; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 495%.
Embodiment 6
(1) preparation of Halogenless composite fire retardant
Formula: in mass parts
40 parts of palygorskite clay, 52 parts of melamine phosphates, 8 parts of cenospheres.
Technique: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
First utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, 40 parts of the Halogenless composite fire retardants of modification are mixed with 100 parts of thermoplastic elastomer EVA, adopt twin-screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material EVA.Above-mentioned fire retardant and EVA are in mass parts.
The performance of flame retardant resistance matrix material EVA: oxygen index: 36; Under the nonflame condition, smoke density 290; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 342%.
Claims (1)
1. a Halogenless composite fire retardant, is characterized in that: be to be that raw material mixes by palygorskite clay, melamine phosphate and cenosphere; Described palygorskite clay, melamine phosphate and cenosphere are pressed following proportion by weight:
40 parts of palygorskite clay, 40 ~ 55 parts of melamine phosphates, 20 ~ 5 parts of cenospheres.
2, the application of Halogenless composite fire retardant in the preparation flame retardant thermoplastic elastomer composite material as claimed in claim 1.
3, the application of Halogenless composite fire retardant in the preparation flame retardant thermoplastic elastomer composite material as claimed in claim 2, it is characterized in that: first utilize ordinary method to carry out organic modification to the Halogenless composite fire retardant surface, then the Halogenless composite fire retardant after modification and thermoplastic elastomer mixed melting are extruded; The add-on of fire retardant is 20 ~ 50% of thermoplastic elastic weight.
4, the application of Halogenless composite fire retardant in the preparation flame retardant thermoplastic elastomer composite material as claimed in claim 3, it is characterized in that: described thermoplastic elastomer is alkenes compounds, polyvinyl chloride-base compound, ammonia ester compound, ester compound, amides, organic fluorine compounds.
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| CN103172938B (en) * | 2013-04-17 | 2015-05-13 | 西北师范大学 | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material |
| CN104072977B (en) * | 2013-06-17 | 2017-07-07 | 青岛科技大学 | A kind of flame retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN103540064B (en) * | 2013-10-29 | 2015-12-30 | 绿宝电缆（集团）有限公司 | The flame-retardant modified polyvinyl chloride cable sheathing compound of a kind of oil resistant |
| WO2017005546A1 (en) | 2015-07-09 | 2017-01-12 | Danmarks Tekniske Universitet | Fire retardant formulations |
| CN108641122B (en) * | 2018-04-18 | 2019-03-29 | 西北师范大学 | A kind of palygorskite Quito functional polymer material auxiliary agent and preparation method thereof |
| CN110105767A (en) * | 2019-05-31 | 2019-08-09 | 昆山兆科电子材料有限公司 | A kind of heat conductive flame-retarding insulating materials |
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| CN100350015C (en) * | 2005-01-18 | 2007-11-21 | 西北师范大学 | Palygorskite compound flame retardant |
| CN101284919A (en) * | 2008-05-09 | 2008-10-15 | 西北师范大学 | Paligorskite-butadiene styrene rubber composite fire retardant material |
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Effective date of registration: 20201208 Address after: No.33 Hengyang South Road, Jinhu County, Huaian City, Jiangsu Province 211600 Patentee after: Jinhu agricultural and sideline products Marketing Association Address before: 730070 Anning Road, Anning District, Gansu, Lanzhou, China, No. 967 Patentee before: Northwest Normal University |