CN102352057A - 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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- CN102352057A CN102352057A CN2011102656026A CN201110265602A CN102352057A CN 102352057 A CN102352057 A CN 102352057A CN 2011102656026 A CN2011102656026 A CN 2011102656026A CN 201110265602 A CN201110265602 A CN 201110265602A CN 102352057 A CN102352057 A CN 102352057A
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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, relating in particular to a kind of is the composite Halogenless composite fire retardant that forms of raw material with palygorskite clay, melamine phosphate and cenosphere, belongs 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 do not need process hot sulfurization as rubber again, thereby use simple plastic processing machinery can process the finished product at an easy rate.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 daily goods such as rubber overshoes, adhesive plaster, various industrial goods and 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 above the modification of engineering plastics such as interchangeable heat plastic resins such as PVC, PE, PP, PS even 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 big harm to the security of the lives and property.Combustionproperty to institute's materials used in China's national standard and the 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 flame-retardant modifiedly to thermoplastic elastomer, make it be applied to every field widely.
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 among the 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 the mechanical property of material in addition yet.People such as the Li Xiaoyan (performance of thermoplastic polyolefin elastomer/primary ammonium phosphate flame retardant composites system; Dalian Polytechnic University's journal; 2010; 29 (2): 137-139) studied the fire retardancy of primary ammonium phosphate to thermoplastic elastomer; But oxygen index has only 25.9, can not satisfy the requirement of country to electric wire and building materials.
Summary of the invention
The object of the invention provides a kind of flame retardant properties good to the problem that exists in the prior art, does not influence the Halogenless composite fire retardant of thermoplastic elastomer mechanical property again.
Another object of the present invention provides 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 materials mix forms 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 with polymer after compound; Polygorskite hardness is processed into the nano-micrometre grade particles easily 2 ~ 2.5; The microvoid structure of polygorskite; Make it strong adsorption arranged to gas; The heat insulation thermal insulation of hollow 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 the nuisanceless fire retardant material of a kind of ideal.
Melamine phosphate can decompose the oxygen acid that produces ammonia and phosphorus when being heated, ammonia can dilute the concentration of gases such as inflammable gas and airborne oxygen, thereby it stops the incendiary effect.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 the 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, sphere, has hard shell at good fluidity, hollow; Cenosphere belongs to manosil AS class inorganic powder material, and major ingredient is SiO
2And Al
2O
3, be described as " Space Age material ".Because the cenosphere heat-drawn wire is 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 that three's fire retardation cooperatively interacts, 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 each material component is by following weight part proportioning in the composite flame-retardant agent, and composite flame-retardant agent all has the good flame performance:
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 a thermoplastic elastomer quality.
For resistance of aging and the processing characteristics that improves thermoplastic elastomer; In melting process; Also can add some processing aids, like 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 the prior art.
Said 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; Two-(the silica-based propyl group of γ-triethoxy) tetrasulfide and sooty mixture (1:1); 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-An Bingjisanjiayangjiguiwan; γ-An Bingjisanyiyangjiguiwan; Titante coupling agent; Zirconate class coupling agent; Aluminium esters of gallic acid coupling agent; Stearic acid, Zinic stearas, calcium stearate, the mixture of one or more in the barium stearate.
Said thermoplastic elastomer has: styrene compound (like 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 added cenosphere, be used to prepare flame retardant thermoplastic elastomer composite material in the composite flame-retardant agent of the present invention, not only improved the flame retardant properties of matrix material, and made matrix material have the good processing flowability ability.
Embodiment
Through specific embodiment detailed explanation is done in the preparation of composite flame-retardant agent of the present invention, flame-retardant thermoplastic elastomer and the performance of thermoplastic elastomer below.
Embodiment 1
(1) preparation of Halogenless composite fire retardant
Prescription: in mass parts
40 parts of palygorskite clay, 43 parts of melamine phosphates, 17 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, 45 parts of the Halogenless composite fire retardants of modification are mixed with thermoplastic elastomer TPO100 part, adopt the 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; Smoke density 280 under the nonflame condition; 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
Prescription: in mass parts
40 parts of palygorskite clay, 48 parts of melamine phosphates, 12 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, again with modification 35 parts of Halogenless composite fire retardants mix for 100 parts with thermoplastic elastomer TPU, adopt the 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; Smoke density 265 under the nonflame condition; 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
Prescription: in mass parts
40 parts of palygorskite clay, 50 parts of melamine phosphates, 10 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, 50 parts of the Halogenless composite fire retardants of modification are mixed for 100 parts with thermoplastic elastomer TPV, adopt the 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; Smoke density 244 under the nonflame condition; 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
Prescription: in mass parts
40 parts of palygorskite clay, 40 parts of melamine phosphates, 20 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier,, adopt the twin screw extrusion equipment to melt extrude, obtain flame retardant resistance matrix material SEBS in that 40 parts of the Halogenless composite fire retardants of modification are mixed for 100 parts with thermoplastic elastomer SEBS.Above-mentioned fire retardant and SEBS are in mass parts.
The performance of flame retardant resistance matrix material SEBS: oxygen index: 32; Smoke density 287 under the nonflame condition; 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
Prescription: in mass parts
40 parts of palygorskite clay, 55 parts of melamine phosphates, 5 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, again 20 parts of the Halogenless composite fire retardants of modification are mixed for 100 parts with thermoplastic elastomer PBT, adopt the 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; Smoke density 279 under the nonflame condition; 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
Prescription: in mass parts
40 parts of palygorskite clay, 52 parts of melamine phosphates, 8 parts of cenospheres.
Technology: palygorskite clay, melamine phosphate and the cenosphere mode with mechanical blending is mixed.
(2) preparation of flame-retardant thermoplastic elastomer
Utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, 40 parts of the Halogenless composite fire retardants of modification are mixed for 100 parts with thermoplastic elastomer EVA, adopt the 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; Smoke density 290 under the nonflame condition; Horizontal firing reaches the FH-1 rank, and vertical combustion reaches the FV-0 rank; Elongation at break is 342%.
Claims (5)
1. Halogenless composite fire retardant is characterized in that: be to be that raw materials mix forms by palygorskite clay, melamine phosphate and cenosphere.
2. Halogenless composite fire retardant according to claim 1 is characterized in that: said palygorskite clay, melamine phosphate and cenosphere are by following proportion by weight:
40 parts of palygorskite clay, 40 ~ 55 parts of melamine phosphates, 20 ~ 5 parts of cenospheres.
3. the application of Halogenless composite fire retardant in the preparation flame retardant thermoplastic elastomer composite material according to claim 1.
4. like the application of Halogenless composite fire retardant as described in the claim 3 in the preparation flame retardant thermoplastic elastomer composite material; It is characterized in that: utilize ordinary method that organic modification is carried out on the Halogenless composite fire retardant surface earlier, then Halogenless composite fire retardant after the modification and thermoplastic elastomer mixed melting are extruded; The add-on of fire retardant is 20 ~ 50% of a thermoplastic elastomer quality.
5. like the application of Halogenless composite fire retardant as described in the claim 4 in the preparation flame retardant thermoplastic elastomer composite material, it is characterized in that: said thermoplastic elastomer is styrene compound, alkenes compounds, double vinyl compound, polyvinyl chloride-base compound, ammonia ester compound, ester compound, amides, organic fluorine compounds.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172938A (en) * | 2013-04-17 | 2013-06-26 | 西北师范大学 | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material |
| CN103540064A (en) * | 2013-10-29 | 2014-01-29 | 绿宝电缆（集团）有限公司 | Oil-proof flame-retardant modified polyvinyl chloride cable sheathing material |
| WO2017005546A1 (en) | 2015-07-09 | 2017-01-12 | Danmarks Tekniske Universitet | Fire retardant formulations |
| 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 |
| CN108641122A (en) * | 2018-04-18 | 2018-10-12 | 西北师范大学 | A kind of palygorskite Quito functional high molecule 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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| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
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| CN1654599A (en) * | 2005-01-18 | 2005-08-17 | 西北师范大学 | Palygorskite compound flame retardant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172938A (en) * | 2013-04-17 | 2013-06-26 | 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 |
| CN103540064A (en) * | 2013-10-29 | 2014-01-29 | 绿宝电缆（集团）有限公司 | Oil-proof flame-retardant modified polyvinyl chloride cable sheathing material |
| 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 |
| CN108641122A (en) * | 2018-04-18 | 2018-10-12 | 西北师范大学 | A kind of palygorskite Quito functional high molecule material auxiliary agent and preparation method thereof |
| 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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